Sample records for copper transporting p-type

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. Molecular Diagnostics of Copper-Transporting Protein Mutations Allows Early Onset Individual Therapy of Menkes Disease.

    PubMed

    Králík, L; Flachsová, E; Hansíková, H; Saudek, V; Zeman, J; Martásek, P

    2017-01-01

    Menkes disease is a severe X-linked recessive disorder caused by a defect in the ATP7A gene, which encodes a membrane copper-transporting ATPase. Deficient activity of the ATP7A protein results in decreased intestinal absorption of copper, low copper level in serum and defective distribution of copper in tissues. The clinical symptoms are caused by decreased activities of copper-dependent enzymes and include neurodegeneration, connective tissue disorders, arterial changes and hair abnormalities. Without therapy, the disease is fatal in early infancy. Rapid diagnosis of Menkes disease and early start of copper therapy is critical for the effectiveness of treatment. We report a molecular biology-based strategy that allows early diagnosis of copper transport defects and implementation of individual therapies before the full development of pathological symptoms. Low serum copper and decreased activity of copperdependent mitochondrial cytochrome c oxidase in isolated platelets found in three patients indicated a possibility of functional defects in copper-transporting proteins, especially in the ATPA7 protein, a copper- transporting P-type ATPase. Rapid mutational screening of the ATP7A gene using high-resolution melting analysis of DNA indicated presence of mutations in the patients. Molecular investigation for mutations in the ATP7A gene revealed three nonsense mutations: c.2170C>T (p.Gln724Ter); c.3745G>T (p.Glu1249Ter); and c.3862C>T (p.Gln1288Ter). The mutation c.3745G>T (p.Glu1249Ter) has not been identified previously. Molecular analysis of the ATOX1 gene as a possible modulating factor of Menkes disease did not reveal presence of pathogenic mutations. Molecular diagnostics allowed early onset of individual therapies, adequate genetic counselling and prenatal diagnosis in the affected families.

  6. 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 .

  7. 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...

  8. 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

  9. 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

  10. A Plasmodium falciparum copper-binding membrane protein with copper transport motifs

    PubMed Central

    2012-01-01

    Background Copper is an essential catalytic co-factor for metabolically important cellular enzymes, such as cytochrome-c oxidase. Eukaryotic cells acquire copper through a copper transport protein and distribute intracellular copper using molecular chaperones. The copper chelator, neocuproine, inhibits Plasmodium falciparum ring-to-trophozoite transition in vitro, indicating a copper requirement for malaria parasite development. How the malaria parasite acquires or secretes copper still remains to be fully elucidated. Methods PlasmoDB was searched for sequences corresponding to candidate P. falciparum copper-requiring proteins. The amino terminal domain of a putative P. falciparum copper transport protein was cloned and expressed as a maltose binding fusion protein. The copper binding ability of this protein was examined. Copper transport protein-specific anti-peptide antibodies were generated in chickens and used to establish native protein localization in P. falciparum parasites by immunofluorescence microscopy. Results Six P. falciparum copper-requiring protein orthologs and a candidate P. falciparum copper transport protein (PF14_0369), containing characteristic copper transport protein features, were identified in PlasmoDB. The recombinant amino terminal domain of the transport protein bound reduced copper in vitro and within Escherichia coli cells during recombinant expression. Immunolocalization studies tracked the copper binding protein translocating from the erythrocyte plasma membrane in early ring stage to a parasite membrane as the parasites developed to schizonts. The protein appears to be a PEXEL-negative membrane protein. Conclusion Plasmodium falciparum parasites express a native protein with copper transporter characteristics that binds copper in vitro. Localization of the protein to the erythrocyte and parasite plasma membranes could provide a mechanism for the delivery of novel anti-malarial compounds. PMID:23190769

  11. 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

  12. 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.

  13. 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.

  14. Biochemical characterization of P-type copper ATPases

    PubMed Central

    Inesi, Giuseppe; Pilankatta, Rajendra; Tadini-Buoninsegni, Francesco

    2014-01-01

    Copper ATPases, in analogy with other members of the P-ATPase superfamily, contain a catalytic headpiece including an aspartate residue reacting with ATP to form a phosphoenzyme intermediate, and transmembrane helices containing cation-binding sites [TMBS (transmembrane metal-binding sites)] for catalytic activation and cation translocation. Following phosphoenzyme formation by utilization of ATP, bound copper undergoes displacement from the TMBS to the lumenal membrane surface, with no H+ exchange. Although PII-type ATPases sustain active transport of alkali/alkali-earth ions (i.e. Na+, Ca2+) against electrochemical gradients across defined membranes, PIB-type ATPases transfer transition metal ions (i.e. Cu+) from delivery to acceptor proteins and, prominently in mammalian cells, undergo trafficking from/to various membrane compartments. A specific component of copper ATPases is the NMBD (N-terminal metal-binding domain), containing up to six copper-binding sites in mammalian (ATP7A and ATP7B) enzymes. Copper occupancy of NMBD sites and interaction with the ATPase headpiece are required for catalytic activation. Furthermore, in the presence of copper, the NMBD allows interaction with protein kinase D, yielding phosphorylation of serine residues, ATP7B trafficking and protection from proteasome degradation. A specific feature of ATP7A is glycosylation and stabilization on plasma membranes. Cisplatin, a platinum-containing anti-cancer drug, binds to copper sites of ATP7A and ATP7B, and undergoes vectorial displacement in analogy with copper. PMID:25242165

  15. Copper tolerance mediated by polyphosphate degradation and low-affinity inorganic phosphate transport system in Escherichia coli.

    PubMed

    Grillo-Puertas, Mariana; Schurig-Briccio, Lici Ariane; Rodríguez-Montelongo, Luisa; Rintoul, María Regina; Rapisarda, Viviana Andrea

    2014-03-19

    Metal tolerance in bacteria has been related to polyP in a model in which heavy metals stimulate the polymer hydrolysis, forming metal-phosphate complexes that are exported. As previously described in our laboratory, Escherichia coli cells grown in media containing a phosphate concentration >37 mM maintained an unusually high polyphosphate (polyP) level in stationary phase. The aim of the present work was to evaluate the influence of polyP levels as the involvement of low-affinity inorganic phosphate transport (Pit) system in E. coli copper tolerance. PolyP levels were modulated by the media phosphate concentration and/or using mutants in polyP metabolism. Stationary phase wild-type cells grown in high phosphate medium were significantly more tolerant to copper than those grown in sufficient phosphate medium. Copper addition to tolerant cells induced polyP degradation by PPX (an exopolyphosphatase), phosphate efflux and membrane polarization. ppk-ppx- (unable to synthesize/degrade polyP), ppx- (unable to degrade polyP) and Pit system mutants were highly sensitive to metal even in high phosphate media. In exponential phase, CopA and polyP-Pit system would act simultaneously to detoxify the metal or one could be sufficient to safeguard the absence of the other. Our results support a mechanism for copper detoxification in exponential and stationary phases of E. coli, involving Pit system and degradation of polyP. Data reflect the importance of the environmental phosphate concentration in the regulation of the microbial physiological state.

  16. The gene ICS3 from the yeast Saccharomyces cerevisiae is involved in copper homeostasis dependent on extracellular pH.

    PubMed

    Alesso, C A; Discola, K F; Monteiro, G

    2015-09-01

    In the yeast Saccharomyces cerevisiae, many genes are involved in the uptake, transport, storage and detoxification of copper. Large scale studies have noted that deletion of the gene ICS3 increases sensitivity to copper, Sortin 2 and acid exposure. Here, we report a study on the Δics3 strain, in which ICS3 is related to copper homeostasis, affecting the intracellular accumulation of this metal. This strain is sensitive to hydrogen peroxide and copper exposure, but not to other tested transition metals. At pH 6.0, the Δics3 strain accumulates a larger amount of intracellular copper than the wild-type strain, explaining the sensitivity to oxidants in this condition. Unexpectedly, sensitivity to copper exposure only occurs in acidic conditions. This can be explained by the fact that the exposure of Δics3 cells to high copper concentrations at pH 4.0 results in over-accumulation of copper and iron. Moreover, the expression of ICS3 increases in acidic pH, and this is correlated with CCC2 gene expression, since both genes are regulated by Rim101 from the pH regulon. CCC2 is also upregulated in Δics3 in acidic pH. Together, these data indicate that ICS3 is involved in copper homeostasis and is dependent on extracellular pH. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Functional analysis of mutations in the ATP loop of the Wilson disease copper transporter, ATP7B.

    PubMed

    Luoma, Leiah M; Deeb, Taha M M; Macintyre, Georgina; Cox, Diane W

    2010-05-01

    Wilson disease (WND) is an autosomal recessive disorder resulting from mutation of ATP7B. Transport of copper by ATP7B from the trans-Golgi of hepatocytes into apical membrane-trafficked vesicles for excretion in the bile is the major means of copper elimination from the body. Although copper is an essential nutrient, homeostasis must be carefully maintained. If homeostasis is disrupted, copper can accumulate within the liver, kidney, cornea, and/or brain. The range of organs affected leads to clinical heterogeneity and difficulty in WND diagnosis. Sequencing of ATP7B is an important adjunct for diagnosis but has led to the discovery of many novel missense variants. Although prediction programs are available, functional characterization is essential for determining the consequence of novel variants. We have tested 12 missense variants localized to the ATP loop of ATP7B and compared three predictive programs (SIFT, PolyPhen, and Align-GVGD). We found p.L1043P, p.G1000R, p.G1101R, p.I1102T, p.V1239G, and p.D1267V deleterious; p.G1176E and p.G1287S intermediate; p.E1173G temperature sensitive; p.T991M and p.I1148T mild; and p.R1228T functioning as wild type. We found that SIFT most often agreed with functional data (92%), compared with PolyPhen (83%) and Align-GVGD (67%). We conclude that variants found to negatively affect function likely contribute to the WND phenotype in patients. (c) 2010 Wiley-Liss, Inc.

  18. 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.

  19. The interplay between siderophore secretion and coupled iron and copper transport in the heterocyst-forming cyanobacterium Anabaena sp. PCC 7120.

    PubMed

    Nicolaisen, Kerstin; Hahn, Alexander; Valdebenito, Marianne; Moslavac, Suncana; Samborski, Anastazia; Maldener, Iris; Wilken, Corinna; Valladares, Ana; Flores, Enrique; Hantke, Klaus; Schleiff, Enrico

    2010-11-01

    Iron uptake is essential for Gram-negative bacteria including cyanobacteria. In cyanobacteria, however, the iron demand is higher than in proteobacteria due to the function of iron as a cofactor in photosynthesis and nitrogen fixation, but our understanding of iron uptake by cyanobacteria stands behind the knowledge in proteobacteria. Here, two genes involved in this process in the heterocyst-forming cyanobacterium Anabaena sp. PCC 7120 were identified. ORF all4025 encodes SchE, a putative cytoplasmic membrane-localized transporter involved in TolC-dependent siderophore secretion. Inactivation of schE resulted in an enhanced sensitivity to high metal concentrations and decreased secretion of hydroxamate-type siderophores. ORF all4026 encodes a predicted outer membrane-localized TonB-dependent iron transporter, IacT. Inactivation of iacT resulted in decreased sensitivity to elevated iron and copper levels. Expression of iacT from the artificial trc promoter (P(trc)) resulted in sensitization against tested metals. Further analysis showed that iron and copper effects are synergistic because a decreased supply of iron induced a significant decrease of copper levels in the iacT insertion mutant but an increase of those levels in the strain carrying P(trc)-iacT. Our results unravel a link between iron and copper homeostasis in Anabaena sp. PCC 7120. Copyright © 2010 Elsevier B.V. All rights reserved.

  20. 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.

  1. High-affinity copper transport and Snq2 export permease of saccharomyces cerevisiae modulate cytotoxicity of PR-10 from Theobroma cacao.

    PubMed

    Pungartnik, Cristina; da Silva, Aline Clara; de Melo, Sarah Alves; Gramacho, Karina Peres; de Mattos Cascardo, Júlio Cézar; Brendel, Martin; Micheli, Fabienne; da Silva Gesteira, Abelmon

    2009-01-01

    A pathogenesis-related (PR) protein from Theobroma cacao (TcPR-10) was identified from a cacao-Moniliophthora perniciosa interaction cDNA library. Nucleotide and amino acid sequences showed homology with other PR-10 proteins having P loop motif and Betv1 domain. Recombinant TcPR-10 showed in vitro and in vivo ribonuclease activity, and antifungal activity against the basidiomycete cacao pathogen M. perniciosa and the yeast Saccharomyces cerevisiae. Fluorescein isothiocyanate-labeled TcPR-10 was internalized by M. perniciosa hyphae and S. cerevisiae cells and inhibited growth of both fungi. Energy and temperature-dependent internalization of the TcPR-10 suggested an active importation into the fungal cells. Chronical exposure to TcPR-10 of 29 yeast mutants with single gene defects in DNA repair, general membrane transport, metal transport, and antioxidant defenses was tested. Two yeast mutants were hyperresistant compared with their respective isogenic wild type: ctr3Delta mutant, lacking the high-affinity plasma membrane copper transporter and mac1Delta, the copper-sensing transcription factor involved in regulation of high-affinity copper transport. Acute exposure of exponentially growing yeast cells revealed that TcPR-10 resistance is also enhanced in the Snq2 export permease-lacking mutant which has reduced intracellular presence of TcPR-10.

  2. 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.

  3. COPT6 Is a Plasma Membrane Transporter That Functions in Copper Homeostasis in Arabidopsis and Is a Novel Target of SQUAMOSA Promoter-binding Protein-like 7*

    PubMed Central

    Jung, Ha-il; Gayomba, Sheena R.; Rutzke, Michael A.; Craft, Eric; Kochian, Leon V.; Vatamaniuk, Olena K.

    2012-01-01

    Among the mechanisms controlling copper homeostasis in plants is the regulation of its uptake and tissue partitioning. Here we characterized a newly identified member of the conserved CTR/COPT family of copper transporters in Arabidopsis thaliana, COPT6. We showed that COPT6 resides at the plasma membrane and mediates copper accumulation when expressed in the Saccharomyces cerevisiae copper uptake mutant. Although the primary sequence of COPT6 contains the family conserved domains, including methionine-rich motifs in the extracellular N-terminal domain and a second transmembrane helix (TM2), it is different from the founding family member, S. cerevisiae Ctr1p. This conclusion was based on the finding that although the positionally conserved Met106 residue in the TM2 of COPT6 is functionally essential, the conserved Met27 in the N-terminal domain is not. Structure-function studies revealed that the N-terminal domain is dispensable for COPT6 function in copper-replete conditions but is important under copper-limiting conditions. In addition, COPT6 interacts with itself and with its homolog, COPT1, unlike Ctr1p, which interacts only with itself. Analyses of the expression pattern showed that although COPT6 is expressed in different cell types of different plant organs, the bulk of its expression is located in the vasculature. We also show that COPT6 expression is regulated by copper availability that, in part, is controlled by a master regulator of copper homeostasis, SPL7. Finally, studies using the A. thaliana copt6-1 mutant and plants overexpressing COPT6 revealed its essential role during copper limitation and excess. PMID:22865877

  4. Studies on transport properties of copper doped tungsten diselenide single crystals

    NASA Astrophysics Data System (ADS)

    Deshpande, M. P.; Parmar, M. N.; Pandya, Nilesh N.; Chaki, Sunil; Bhatt, Sandip V.

    2012-02-01

    During recent years, transition metal dichalcogenides of groups IVB, VB and VIB have received considerable attention because of the great diversity in their transport properties. 2H-WSe 2 (Tungsten diselenide) is an interesting member of the transition metal dichalcogenide (TMDC's) family and known to be a semiconductor useful for photovoltaic and optoelectronic applications. The anisotropy usually observed in this diamagnetic semiconductor material is a result of the sandwich structure of Se-W-Se layers interacting with each other, loosely bonded by the weak Van der Waals forces. Recent efforts in studying the influence of the anisotropic electrical and optical properties of this layered-type transition metal dichalcogenides have been implemented by doping the samples with different alkali group elements. Unfortunately, little work is reported on doping of metals in WSe 2. Therefore, it is proposed in this work to carry out a systematic growth of single crystals of WSe 2 by doping it with copper in different proportions i.e. Cu xWSe 2 ( x=0, 0.5, 1.0) by direct vapour transport technique. Transport properties like low and high temperature resistivity measurements, high pressure resistivity, Seebeck coefficient measurements at low temperature and Hall Effect at room temperature were studied in detail on all these samples. These measurements show that tungsten diselenide single crystals are p-type whereas doped with copper makes it n-type in nature. The results obtained and their implications are discussed in this paper.

  5. 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

  6. 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

  7. Copper-resistant halophilic bacterium isolated from the polluted Maruit Lake, Egypt.

    PubMed

    Osman, O; Tanguichi, H; Ikeda, K; Park, P; Tanabe-Hosoi, S; Nagata, S

    2010-04-01

    To isolate and characterize copper-resistant halophilic bacteria from the polluted Maruit Lake, Egypt and identify the role of plasmids in toxic metal resistance. We isolated strain MA2, showing high copper resistance up to the 1.5 mmol l(-1) concentration; it was also resistant to other metals such as nickel, cobalt and zinc and a group of antibiotics. Partial 16S rRNA analysis revealed that strain MA2 belonged to the genus Halomonas. Copper uptake, measured by atomic absorption spectrophotometery, was higher in the absence of NaCl than in the presence of 0.5-1.0 mol l(-1) NaCl during 5-15 min of incubation. Cell fractionation and electron microscopic observation clarified that most of the copper accumulated in the outer membrane and periplasmic fractions of the cells. Plasmid screening yielded two plasmids: pMA21 (11 kb) and pMA22 (5 kb). Plasmid curing resulted in a strain that lost both the plasmids and was sensitive to cobalt and chromate but not copper, nickel and zinc. This cured strain also showed weak growth in the presence of 0.5-1.0 mol l(-1) NaCl. Partial sequencing of both plasmids led to the identification of different toxic metals transporters but copper transporters were not identified. The highest cell viability was found in the presence of 1.0 mol l(-1) NaCl at different copper concentrations, and copper uptake was optimal in the absence of NaCl. Plasmid pMA21 encoded chromate, cobalt, zinc and cadmium transporters, whereas pMA22 encoded specific zinc and RND (resistance, nodulation, cell division) efflux transporters as well as different kinds of metabolic enzymes. Copper resistance was mainly incorporated in the chromosome. Strain MA2 is a fast and efficient tool for copper bioremediation and the isolated plasmids show significant characteristics of both toxic metal and antibiotic resistance.

  8. 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

  9. Monitoring Interactions Inside Cells by Advanced Spectroscopies: Overview of Copper Transporters and Cisplatin.

    PubMed

    Lasorsa, Alessia; Natile, Giovanni; Rosato, Antonio; Tadini-Buoninsegni, Francesco; Arnesano, Fabio

    2018-02-12

    Resistance, either at the onset of the treatment or developed after an initial positive response, is a major limitation of antitumor therapy. In the case of platinum- based drugs, copper transporters have been found to interfere with drug trafficking by facilitating the import or favoring the platinum export and inactivation. The use of powerful spectroscopic, spectrometric and computational methods has allowed a deep structural insight into the mode of interaction of platinum drugs with the metal-binding domains of the transporter proteins. This review article focuses on the mode in which platinum drugs can compete with copper ion for binding to transport proteins and consequent structural and biological effects. Three types of transporters are discussed in detail: copper transporter 1 (Ctr1), the major responsible for Cu+ uptake; antioxidant-1 copper chaperone (Atox1), responsible for copper transfer within the cytoplasm; and copper ATPases (ATP7A/B), responsible for copper export into specific subcellular compartments and outside the cell. The body of knowledge summarized in this review can help in shaping current chemotherapy to optimize the efficacy of platinum drugs (particularly in relation to resistance) and to mitigate adverse effects on copper metabolism. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  10. Low resistance Ohmic contact to p-type crystalline silicon via nitrogen-doped copper oxide films

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

    Zhang, Xinyu, E-mail: xinyu.zhang@anu.edu.au; Wan, Yimao; Bullock, James

    2016-08-01

    This work explores the application of transparent nitrogen doped copper oxide (CuO{sub x}:N) films deposited by reactive sputtering to create hole-selective contacts for p-type crystalline silicon (c-Si) solar cells. It is found that CuO{sub x}:N sputtered directly onto crystalline silicon is able to form an Ohmic contact. X-ray photoelectron spectroscopy and Raman spectroscopy measurements are used to characterise the structural and physical properties of the CuO{sub x}:N films. Both the oxygen flow rate and the substrate temperature during deposition have a significant impact on the film composition, as well as on the resulting contact resistivity. After optimization, a low contactmore » resistivity of ∼10 mΩ cm{sup 2} has been established. This result offers significant advantages over conventional contact structures in terms of carrier transport and device fabrication.« less

  11. ATP7A Gene Addition to the Choroid Plexus Results in Long-term Rescue of the Lethal Copper Transport Defect in a Menkes Disease Mouse Model

    PubMed Central

    Donsante, Anthony; Yi, Ling; Zerfas, Patricia M; Brinster, Lauren R; Sullivan, Patricia; Goldstein, David S; Prohaska, Joseph; Centeno, Jose A; Rushing, Elisabeth; Kaler, Stephen G

    2011-01-01

    Menkes disease is a lethal infantile neurodegenerative disorder of copper metabolism caused by mutations in a P-type ATPase, ATP7A. Currently available treatment (daily subcutaneous copper injections) is not entirely effective in the majority of affected individuals. The mottled-brindled (mo-br) mouse recapitulates the Menkes phenotype, including abnormal copper transport to the brain owing to mutation in the murine homolog, Atp7a, and dies by 14 days of age. We documented that mo-br mice on C57BL/6 background were not rescued by peripheral copper administration, and used this model to evaluate brain-directed therapies. Neonatal mo-br mice received lateral ventricle injections of either adeno-associated virus serotype 5 (AAV5) harboring a reduced-size human ATP7A (rsATP7A) complementary DNA (cDNA), copper chloride, or both. AAV5-rsATP7A showed selective transduction of choroid plexus epithelia and AAV5-rsATP7A plus copper combination treatment rescued mo-br mice; 86% survived to weaning (21 days), median survival increased to 43 days, 37% lived beyond 100 days, and 22% survived to the study end point (300 days). This synergistic treatment effect correlated with increased brain copper levels, enhanced activity of dopamine-β-hydroxylase, a copper-dependent enzyme, and correction of brain pathology. Our findings provide the first definitive evidence that gene therapy may have clinical utility in the treatment of Menkes disease. PMID:21878905

  12. 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.

  13. Increased copper toxicity in Saccharomyces cerevisiae lacking VPS35, a component of the retromer and monogenic Parkinson disease gene in humans.

    PubMed

    Sowada, Nadine; Stiller, Barbara; Kubisch, Christian

    2016-08-05

    The Saccharomyces cerevisiae gene VPS35 encodes a component of the retromer complex which is involved in vesicle transport from endosomes to the trans-Golgi network. Yeast and human VPS35 orthologs are highly conserved and mutations in human VPS35 cause an autosomal dominant form of late-onset Parkinson disease (PD). We now show that deletion of VPS35 in yeast (vps35Δ) leads to a dose-dependent growth defect towards copper. This increased sensitivity could be rescued by transformation with yeast wild-type VPS35 but not by the expression of a construct harboring the yeast equivalent (i.e. D686N) of the most commonly identified VPS35-associated PD mutation, p.D620N. In addition, we show that expression of one copy of α-synuclein, which is known to directly interact with copper, leads to a pronounced aggravation of copper toxicity in vps35Δ cells, thereby linking the regulation of copper homeostasis by Vps35p in yeast to one of the key molecules in PD pathophysiology. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Membrane-Associated Transporter Protein (MATP) Regulates Melanosomal pH and Influences Tyrosinase Activity

    PubMed Central

    Bin, Bum-Ho; Bhin, Jinhyuk; Yang, Seung Ha; Shin, Misun; Nam, Yeon-Ju; Choi, Dong-Hwa; Shin, Dong Wook; Lee, Ai-Young; Hwang, Daehee; Cho, Eun-Gyung; Lee, Tae Ryong

    2015-01-01

    The SLC45A2 gene encodes a Membrane-Associated Transporter Protein (MATP). Mutations of this gene cause oculocutaneous albinism type 4 (OCA4). However, the molecular mechanism of its action in melanogenesis has not been elucidated. Here, we discuss the role of MATP in melanin production. The SLC45A2 gene is highly enriched in human melanocytes and melanoma cell lines, and its protein, MATP, is located in melanosomes. The knockdown of MATP using siRNAs reduced melanin content and tyrosinase activity without any morphological change in melanosomes or the expression of melanogenesis-related proteins. Interestingly, the knockdown of MATP significantly lowered the melanosomal pH, as verified through DAMP analysis, suggesting that MATP regulates melanosomal pH and therefore affects tyrosinase activity. Finally, we found that the reduction of tyrosinase activity associated with the knockdown of MATP was readily recovered by copper treatment in the in vitro L-DOPA oxidase activity assay of tyrosinase. Considering that copper is an important element for tyrosinase activity and that its binding to tyrosinase depends on melanosomal pH, MATP may play an important role in regulating tyrosinase activity via controlling melanosomal pH. PMID:26057890

  15. 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.

  16. 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.

  17. Fate and Transport of Elemental Copper (Cu0) Nanoparticles through Saturated Porous Media in the Presence of Organic Materials

    EPA Science Inventory

    Column experiments were performed to assess the fate and transport of nanoscale elemental copper (Cu0) particles in saturated quartz sands. Both effluent concentrations and retention profiles were measured over a broad range of physicochemical conditions, which included pH, ionic...

  18. Copper and ectopic expression of the Arabidopsis transport protein COPT1 alter iron homeostasis in rice (Oryza sativa L.).

    PubMed

    Andrés-Bordería, Amparo; Andrés, Fernando; Garcia-Molina, Antoni; Perea-García, Ana; Domingo, Concha; Puig, Sergi; Peñarrubia, Lola

    2017-09-01

    Copper deficiency and excess differentially affect iron homeostasis in rice and overexpression of the Arabidopsis high-affinity copper transporter COPT1 slightly increases endogenous iron concentration in rice grains. Higher plants have developed sophisticated mechanisms to efficiently acquire and use micronutrients such as copper and iron. However, the molecular mechanisms underlying the interaction between both metals remain poorly understood. In the present work, we study the effects produced on iron homeostasis by a wide range of copper concentrations in the growth media and by altered copper transport in Oryza sativa plants. Gene expression profiles in rice seedlings grown under copper excess show an altered expression of genes involved in iron homeostasis compared to standard control conditions. Thus, ferritin OsFER2 and ferredoxin OsFd1 mRNAs are down-regulated whereas the transcriptional iron regulator OsIRO2 and the nicotianamine synthase OsNAS2 mRNAs rise under copper excess. As expected, the expression of OsCOPT1, which encodes a high-affinity copper transport protein, as well as other copper-deficiency markers are down-regulated by copper. Furthermore, we show that Arabidopsis COPT1 overexpression (C1 OE ) in rice causes root shortening in high copper conditions and under iron deficiency. C1 OE rice plants modify the expression of the putative iron-sensing factors OsHRZ1 and OsHRZ2 and enhance the expression of OsIRO2 under copper excess, which suggests a role of copper transport in iron signaling. Importantly, the C1 OE rice plants grown on soil contain higher endogenous iron concentration than wild-type plants in both brown and white grains. Collectively, these results highlight the effects of rice copper status on iron homeostasis, which should be considered to obtain crops with optimized nutrient concentrations in edible parts.

  19. Diabetic cardiomyopathy is associated with defective myocellular copper regulation and both defects are rectified by divalent copper chelation

    PubMed Central

    2014-01-01

    Background Heart disease is the leading cause of death in diabetic patients, and defective copper metabolism may play important roles in the pathogenesis of diabetic cardiomyopathy (DCM). The present study sought to determine how myocardial copper status and key copper-proteins might become impaired by diabetes, and how they respond to treatment with the Cu (II)-selective chelator triethylenetetramine (TETA) in DCM. Methods Experiments were performed in Wistar rats with streptozotocin (STZ)-induced diabetes with or without TETA treatment. Cardiac function was analyzed in isolated-perfused working hearts, and myocardial total copper content measured by particle-induced x-ray emission spectroscopy (PIXE) coupled with Rutherford backscattering spectrometry (RBS). Quantitative expression (mRNA and protein) and/or activity of key proteins that mediate LV-tissue-copper binding and transport, were analyzed by combined RT-qPCR, western blotting, immunofluorescence microscopy, and enzyme activity assays. Statistical analysis was performed using Student’s t-tests or ANOVA and p-values of < 0.05 have been considered significant. Results Left-ventricular (LV) copper levels and function were severely depressed in rats following 16-weeks’ diabetes, but both were unexpectedly normalized 8-weeks after treatment with TETA was instituted. Localized myocardial copper deficiency was accompanied by decreased expression and increased polymerization of the copper-responsive transition-metal-binding metallothionein proteins (MT1/MT2), consistent with impaired anti-oxidant defences and elevated susceptibility to pro-oxidant stress. Levels of the high-affinity copper transporter-1 (CTR1) were depressed in diabetes, consistent with impaired membrane copper uptake, and were not modified by TETA which, contrastingly, renormalized myocardial copper and increased levels and cell-membrane localization of the low-affinity copper transporter-2 (CTR2). Diabetes also lowered indexes of intracellular (IC) copper delivery via the copper chaperone for superoxide dismutase (CCS) to its target cuproenzyme, superoxide dismutase-1 (SOD1): this pathway was rectified by TETA treatment, which normalized SOD1 activity with consequent bolstering of anti-oxidant defenses. Furthermore, diabetes depressed levels of additional intracellular copper-transporting proteins, including antioxidant-protein-1 (ATOX1) and copper-transporting-ATPase-2 (ATP7B), whereas TETA elevated copper-transporting-ATPase-1 (ATP7A). Conclusions Myocardial copper deficiency and defective cellular copper transport/trafficking are revealed as key molecular defects underlying LV impairment in diabetes, and TETA-mediated restoration of copper regulation provides a potential new class of therapeutic molecules for DCM. PMID:24927960

  20. Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu 3–xSe 2

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

    Rettie, Alexander J. E.; Sturza, Mihai; Malliakas, Christos D.

    The two-dimensional material KCu 3–xSe 2 was synthesized using both a K 2Se 3 flux and directly from the elements. It crystallizes in the CsAg 3S 2 structure (monoclinic space group C2/m with a = 15.417(3) Å, b = 4.0742(8) Å, c = 8.3190(17) Å, and β = 112.94(3)°), and single-crystal refinement revealed infinite copper-deficient [Cu 3–xSe 2]– layers separated by K + ions. Thermal analysis indicated that KCu 3–xSe 2 melts congruently at ~755 °C. UV–vis spectroscopy showed an optical band gap of ~1.35 eV that is direct in nature, as confirmed by electronic structure calculations. Electronic transport measurementsmore » on single crystals yielded an in-plane resistivity of ~6 × 10 –1 Ω cm at 300 K that has a complex temperature dependence. The results of Seebeck coefficient measurements were consistent with a doped p-type semiconductor (S = +214 μV K –1 at 300 K), with doping being attributed to copper vacancies. Transport is dominated by low-mobility (on the order of 1 cm 2 V –1 s –1) holes caused by relatively flat valence bands with substantial Cu 3d character and a significant concentration of Cu ion vacancy defects (p ~ 10 19 cm –3) in this material. In conclusion, electronic band structure calculations showed that electrons should be significantly more mobile in this structure type.« less

  1. Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu 3–xSe 2

    DOE PAGES

    Rettie, Alexander J. E.; Sturza, Mihai; Malliakas, Christos D.; ...

    2017-06-21

    The two-dimensional material KCu 3–xSe 2 was synthesized using both a K 2Se 3 flux and directly from the elements. It crystallizes in the CsAg 3S 2 structure (monoclinic space group C2/m with a = 15.417(3) Å, b = 4.0742(8) Å, c = 8.3190(17) Å, and β = 112.94(3)°), and single-crystal refinement revealed infinite copper-deficient [Cu 3–xSe 2]– layers separated by K + ions. Thermal analysis indicated that KCu 3–xSe 2 melts congruently at ~755 °C. UV–vis spectroscopy showed an optical band gap of ~1.35 eV that is direct in nature, as confirmed by electronic structure calculations. Electronic transport measurementsmore » on single crystals yielded an in-plane resistivity of ~6 × 10 –1 Ω cm at 300 K that has a complex temperature dependence. The results of Seebeck coefficient measurements were consistent with a doped p-type semiconductor (S = +214 μV K –1 at 300 K), with doping being attributed to copper vacancies. Transport is dominated by low-mobility (on the order of 1 cm 2 V –1 s –1) holes caused by relatively flat valence bands with substantial Cu 3d character and a significant concentration of Cu ion vacancy defects (p ~ 10 19 cm –3) in this material. In conclusion, electronic band structure calculations showed that electrons should be significantly more mobile in this structure type.« less

  2. Inorganic Polyphosphate, Exopolyphosphatase, and Pho84-Like Transporters May Be Involved in Copper Resistance in Metallosphaera sedula DSM 5348T

    PubMed Central

    Rivero, Matías; Torres-Paris, Constanza; Muñoz, Rodrigo; Cabrera, Ricardo; Navarro, Claudio A.

    2018-01-01

    Polyphosphates (PolyP) are linear polymers of orthophosphate residues that have been proposed to participate in metal resistance in bacteria and archaea. In addition of having a CopA/CopB copper efflux system, the thermoacidophilic archaeon Metallosphaera sedula contains electron-dense PolyP-like granules and a putative exopolyphosphatase (PPXMsed, Msed_0891) and four presumed pho84-like phosphate transporters (Msed_0846, Msed_0866, Msed_1094, and Msed_1512) encoded in its genome. In the present report, the existence of a possible PolyP-based copper-resistance mechanism in M. sedula DSM 5348T was evaluated. M. sedula DSM 5348T accumulated high levels of phosphorous in the form of granules, and its growth was affected in the presence of 16 mM copper. PolyP levels were highly reduced after the archaeon was subjected to an 8 mM CuSO4 shift. PPXMsed was purified, and the enzyme was found to hydrolyze PolyP in vitro. Essential residues for catalysis of PPXMsed were E111 and E113 as shown by a site-directed mutagenesis of the implied residues. Furthermore, M. sedula ppx, pho84-like, and copTMA genes were upregulated upon copper exposure, as determined by qRT-PCR analysis. The results obtained support the existence of a PolyP-dependent copper-resistance system that may be of great importance in the adaptation of this thermoacidophilic archaeon to its harsh environment. PMID:29692683

  3. 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.

  4. Recovery of copper and cyanide from waste cyanide solutions using emulsion liquid membrane with LIX 7950 as the carrier.

    PubMed

    Xie, Feng; Wang, Wei

    2017-08-01

    The feasibility of using emulsion liquid membranes (ELMs) with the guanidine extractant LIX 7950 as the mobile carrier for detoxifying copper-containing waste cyanide solutions has been determined. Relatively stable ELMs can be maintained under suitable stirring speed during mixing ELMs and the external solution. Effective extraction of copper cyanides by ELMs only occurs at pH below 11. High copper concentration in the external phase and high volume ratio of the external phase to ELMs result in high transport rates of copper and cyanide. High molar ratio of cyanide to copper tends to suppress copper extraction. The presence of thiocyanate ion significantly depresses the transport of copper and cyanide through the membrane while the thiosulfate ion produces less impact on copper removal by ELMs. Zinc and nickel cyanides can also be effectively extracted by ELMs. More than 90% copper and cyanide can be effectively removed from alkaline cyanide solutions by ELMs under suitable experimental conditions, indicating the effectiveness of using the designed ELM for recovering copper and cyanide from waste cyanide solutions.

  5. Transcriptional response of Erwinia amylovora to copper shock: in vivo role of the copA gene.

    PubMed

    Águila-Clares, Begoña; Castiblanco, Luisa F; Quesada, José Miguel; Penyalver, Ramón; Carbonell, Juan; López, María M; Marco-Noales, Ester; Sundin, George W

    2018-01-01

    Fire blight is a devastating plant disease caused by the bacterium Erwinia amylovora, and its control is frequently based on the use of copper-based compounds whose mechanisms of action are not well known. Consequently, in this article, we investigate the response of E. amylovora to copper shock by a whole-genome microarray approach. Transcriptional analyses showed that, in the presence of copper, 23 genes were increased in expression; these genes were classified mainly into the transport and stress functional categories. Among them, the copA gene was strongly induced and regulated in a finely tuned manner by copper. Mutation of copA, soxS, arcB, yjcE, ygcF, yhhQ, galF and EAM_3469 genes revealed that tolerance to copper in E. amylovora can be achieved by complex physiological mechanisms, including: (i) the control of copper homeostasis through, at least, the extrusion of Cu(I) by a P-type ATPase efflux pump CopA; and (ii) the overcoming of copper toxicity caused by oxidative stress by the expression of several reactive oxygen species (ROS)-related genes, including the two major transcriptional factors SoxS and ArcB. Furthermore, complementation analyses demonstrated the important role of copA for copper tolerance in E. amylovora, not only in vitro, but also in inoculated pear shoots. © 2016 BSPP AND JOHN WILEY & SONS LTD.

  6. Adaptor Protein-1 Complex Affects the Endocytic Trafficking and Function of Peptidylglycine α-Amidating Monooxygenase, a Luminal Cuproenzyme*

    PubMed Central

    Bonnemaison, Mathilde L.; Bäck, Nils; Duffy, Megan E.; Ralle, Martina; Mains, Richard E.; Eipper, Betty A.

    2015-01-01

    The adaptor protein-1 complex (AP-1), which transports cargo between the trans-Golgi network and endosomes, plays a role in the trafficking of Atp7a, a copper-transporting P-type ATPase, and peptidylglycine α-amidating monooxygenase (PAM), a copper-dependent membrane enzyme. Lack of any of the four AP-1 subunits impairs function, and patients with MEDNIK syndrome, a rare genetic disorder caused by lack of expression of the σ1A subunit, exhibit clinical and biochemical signs of impaired copper homeostasis. To explore the role of AP-1 in copper homeostasis in neuroendocrine cells, we used corticotrope tumor cells in which AP-1 function was diminished by reducing expression of its μ1A subunit. Copper levels were unchanged when AP-1 function was impaired, but cellular levels of Atp7a declined slightly. The ability of PAM to function was assessed by monitoring 18-kDa fragment-NH2 production from proopiomelanocortin. Reduced AP-1 function made 18-kDa fragment amidation more sensitive to inhibition by bathocuproine disulfonate, a cell-impermeant Cu(I) chelator. The endocytic trafficking of PAM was altered, and PAM-1 accumulated on the cell surface when AP-1 levels were reduced. Reduced AP-1 function increased the Atp7a presence in early/recycling endosomes but did not alter the ability of copper to stimulate its appearance on the plasma membrane. Co-immunoprecipitation of a small fraction of PAM and Atp7a supports the suggestion that copper can be transferred directly from Atp7a to PAM, a process that can occur only when both proteins are present in the same subcellular compartment. Altered luminal cuproenzyme function may contribute to deficits observed when the AP-1 function is compromised. PMID:26170456

  7. Spontaneous and Directional Bubble Transport on Porous Copper Wires with Complex Shapes in Aqueous Media.

    PubMed

    Li, Wenjing; Zhang, Jingjing; Xue, Zhongxin; Wang, Jingming; Jiang, Lei

    2018-01-24

    Manipulation of gas bubble behaviors is crucial for gas bubble-related applications. Generally, the manipulation of gas bubble behaviors generally takes advantage of their buoyancy force. It is very difficult to control the transportation of gas bubbles in a specific direction. Several approaches have been developed to collect and transport bubbles in aqueous media; however, most reliable and effective manipulation of gas bubbles in aqueous media occurs on the interfaces with simple shapes (i.e., cylinder and cone shapes). Reliable strategies for spontaneous and directional transport of gas bubbles on interfaces with complex shapes remain enormously challenging. Herein, a type of 3D gradient porous network was constructed on copper wire interfaces, with rectangle, wave, and helix shapes. The superhydrophobic copper wires were immersed in water, and continuous and stable gas films then formed on the interfaces. With the assistance of the Laplace pressure gradient between two bubbles, gas bubbles (including microscopic gas bubbles) in the aqueous media were subsequently transported, continuously and directionally, on the copper wires with complex shapes. The small gas bubbles always moved to the larger ones.

  8. Multi-technique approach to assess the effects of microbial biofilms involved in copper plumbing corrosion.

    PubMed

    Vargas, Ignacio T; Alsina, Marco A; Pavissich, Juan P; Jeria, Gustavo A; Pastén, Pablo A; Walczak, Magdalena; Pizarro, Gonzalo E

    2014-06-01

    Microbially influenced corrosion (MIC) is recognized as an unusual and severe type of corrosion that causes costly failures around the world. A microbial biofilm could enhance the copper release from copper plumbing into the water by forming a reactive interface. The biofilm increases the corrosion rate, the mobility of labile copper from its matrix and the detachment of particles enriched with copper under variable shear stress due to flow conditions. MIC is currently considered as a series of interdependent processes occurring at the metal-liquid interface. The presence of a biofilm results in the following effects: (a) the formation of localized microenvironments with distinct pH, dissolved oxygen concentrations, and redox conditions; (b) sorption and desorption of labile copper bonded to organic compounds under changing water chemistry conditions; (c) change in morphology by deposition of solid corrosion by-products; (d) diffusive transport of reactive chemical species from or towards the metal surface; and (e) detachment of scale particles under flow conditions. Using a multi-technique approach that combines pipe and coupon experiments this paper reviews the effects of microbial biofilms on the corrosion of copper plumbing systems, and proposes an integrated conceptual model for this phenomenon supported by new experimental data. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Plastocyanin Controls the Stabilization of the Thylakoid Cu-transporting P-type ATPase PAA2/HMA8 in Response to Low Copper in Arabidopsis*

    PubMed Central

    Tapken, Wiebke; Ravet, Karl; Pilon, Marinus

    2012-01-01

    PAA2/HMA8 (P-type ATPase of Arabidopsis/Heavy-metal-associated 8) is a thylakoid located copper (Cu)-transporter in Arabidopsis thaliana. In tandem with PAA1/HMA6, which is located in the inner chloroplast envelope, it supplies Cu to plastocyanin (PC), an essential cuproenzyme of the photosynthetic machinery. We investigated whether the chloroplast Cu transporters are affected by Cu addition to the growth media. Immunoblots showed that PAA2 protein abundance decreased significantly and specifically when Cu in the media was increased, while PAA1 remained unaffected. The function of SPL7, the transcriptional regulator of Cu homeostasis, was not required for this regulation of PAA2 protein abundance and Cu addition did not affect PAA2 transcript levels, as determined by qRT-PCR. We used the translational inhibitor cycloheximide to analyze turnover and observed that the stability of the PAA2 protein was decreased in plants grown with elevated Cu. Interestingly, PAA2 protein abundance was significantly increased in paa1 mutants, in which the Cu content in the chloroplast is half of that of the wild-type, due to impaired Cu import into the organelle. In contrast in a pc2 insertion mutant, which has strongly reduced plastocyanin expression, the PAA2 protein levels were low regardless of Cu addition to the growth media. Together, these data indicate that plastid Cu levels control PAA2 stability and that plastocyanin, which is the target of PAA2 mediated Cu delivery in thylakoids, is a major determinant of this regulatory mechanism. PMID:22493454

  10. Thermal conversion of Cu4O3 into CuO and Cu2O and the electrical properties of magnetron sputtered Cu4O3 thin films

    NASA Astrophysics Data System (ADS)

    Murali, Dhanya S.; Aryasomayajula, Subrahmanyam

    2018-03-01

    Among the three oxides of copper (CuO, Cu2O, and Cu4O3), Cu4O3 phase (paramelaconite is a natural, and very scarce mineral) is very difficult to synthesize. It contains copper in both + 1 and + 2 valence states, with an average composition Cu2 1+Cu2 2+O3. We have successfully synthesized Cu4O3 phase at room temperature (300 K) by reactive DC magnetron sputtering by controlling the oxygen flow rate (Murali and Subrahmanyam in J Phys D Appl Phys 49:375102, 2016). In the present communication, Cu4O3 thin films are converted to CuO phases by annealing in the air at 680 K and to Cu2O phase when annealed in argon at 720 K; these phase changes are confirmed by temperature-dependent Raman spectroscopy studies. Probably, this is the first report of the conversion of Cu4O3-CuO and Cu2O by thermal annealing. The temperature-dependent (300-200 K) electrical transport properties of Cu4O3 thin films show that the charge transport above 190 K follows Arrhenius-type behavior with activation energy of 0.14 eV. From photo-electron spectroscopy and electrical transport measurements of Cu4O3 thin films, a downward band bending is observed at the surface of the thin film, which shows its p-type semiconducting nature. The successful preparation of phase pure p-type semiconducting Cu4O3 could provide opportunities to further explore its potential applications.

  11. Effect of dietary copper addition on lipid metabolism in rabbits

    PubMed Central

    Lei, Liu; Xiaoyi, Sui; Fuchang, Li

    2017-01-01

    ABSTRACT The present study was conducted to investigate the effect of copper supplementation on lipid metabolism in rabbits. Our study showed dietary copper addition (5-45 mg/kg) increased body mass gain, but decreased fat and liver weights compared with those in the control group (P < 0.05). Copper (45 mg/kg) addition significantly increased the skeletal muscle weight, but inhibited cytoplasmic lipid accumulation in liver, skeletal muscle and adipose tissue (P < 0.05). Compared with the control group, dietary copper addition (45 mg/kg) significantly increased plasma triglyceride levels but decreased very low density lipoprotein levels (P < 0.05). Copper treatment significantly increased gene expression of carnitine palmitoyltransferase (CPT) 1, CPT2 and peroxisome proliferator-activated receptor (PPAR) a in liver (P < 0.05). In skeletal muscle, CPT1, CPT2, fatty acid transport protein, fatty acid-binding protein, and PPARa mRNA as well as phosphorylated AMP-activated protein kinase (AMPK) levels were significantly up-regulated by copper treatment (P < 0.05). Rabbits receiving copper supplementation had higher CPT1, CPT2, PPARa and hormone-sensitive lipase mRNA levels in adipose tissue (P < 0.05). In conclusion, copper promoted skeletal muscle growth and reduced fat accretion. PPARa signaling in liver, skeletal muscle and adipose tissues and AMPK signaling in skeletal muscle tissue were involved in the regulation of lipid metabolism by copper. PMID:28747869

  12. The Menkes and Wilson disease genes counteract in copper toxicosis in Labrador retrievers: a new canine model for copper-metabolism disorders

    PubMed Central

    Fieten, Hille; Gill, Yadvinder; Martin, Alan J.; Concilli, Mafalda; Dirksen, Karen; van Steenbeek, Frank G.; Spee, Bart; van den Ingh, Ted S. G. A. M.; Martens, Ellen C. C. P.; Festa, Paola; Chesi, Giancarlo; van de Sluis, Bart; Houwen, Roderick H. J. H.; Watson, Adrian L.; Aulchenko, Yurii S.; Hodgkinson, Victoria L.; Zhu, Sha; Petris, Michael J.; Polishchuk, Roman S.; Leegwater, Peter A. J.; Rothuizen, Jan

    2016-01-01

    ABSTRACT The deleterious effects of a disrupted copper metabolism are illustrated by hereditary diseases caused by mutations in the genes coding for the copper transporters ATP7A and ATP7B. Menkes disease, involving ATP7A, is a fatal neurodegenerative disorder of copper deficiency. Mutations in ATP7B lead to Wilson disease, which is characterized by a predominantly hepatic copper accumulation. The low incidence and the phenotypic variability of human copper toxicosis hamper identification of causal genes or modifier genes involved in the disease pathogenesis. The Labrador retriever was recently characterized as a new canine model for copper toxicosis. Purebred dogs have reduced genetic variability, which facilitates identification of genes involved in complex heritable traits that might influence phenotype in both humans and dogs. We performed a genome-wide association study in 235 Labrador retrievers and identified two chromosome regions containing ATP7A and ATP7B that were associated with variation in hepatic copper levels. DNA sequence analysis identified missense mutations in each gene. The amino acid substitution ATP7B:p.Arg1453Gln was associated with copper accumulation, whereas the amino acid substitution ATP7A:p.Thr327Ile partly protected against copper accumulation. Confocal microscopy indicated that aberrant copper metabolism upon expression of the ATP7B variant occurred because of mis-localization of the protein in the endoplasmic reticulum. Dermal fibroblasts derived from ATP7A:p.Thr327Ile dogs showed copper accumulation and delayed excretion. We identified the Labrador retriever as the first natural, non-rodent model for ATP7B-associated copper toxicosis. Attenuation of copper accumulation by the ATP7A mutation sheds an interesting light on the interplay of copper transporters in body copper homeostasis and warrants a thorough investigation of ATP7A as a modifier gene in copper-metabolism disorders. The identification of two new functional variants in ATP7A and ATP7B contributes to the biological understanding of protein function, with relevance for future development of therapy. PMID:26747866

  13. 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...

  14. Reactive solute transport in streams: A surface complexation approach for trace metal sorption

    USGS Publications Warehouse

    Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

    1999-01-01

    A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

  15. Transport of Nanoparticles of Zerovalent Copper, Zinc Oxide, and Titanium Dioxide in Saturated Porous Media

    EPA Science Inventory

    Column tests show nanoparticles (NPs) of Cu(0) and ZnO were immobile at neutral pH in saturated sand.They became mobile in the presence of trizma, humic/fulvic, and citric/oxalic/formic acids. Copper NPs were mobile at pH 9. The deposition rates of TiO2 NP aggregates in both KCl ...

  16. The influence of long-term copper contaminated agricultural soil at different pH levels on microbial communities and springtail transcriptional regulation.

    PubMed

    de Boer, Tjalf E; Taş, Neslihan; Braster, Martin; Temminghoff, Erwin J M; Röling, Wilfred F M; Roelofs, Dick

    2012-01-03

    Copper has long been applied for agricultural practises. Like other metals, copper is highly persistent in the environment and biologically active long after its use has ceased. Here we present a unique study on the long-term effects (27 years) of copper and pH on soil microbial communities and on the springtail Folsomia candida an important representative of the soil macrofauna, in an experiment with a full factorial, random block design. Bacterial communities were mostly affected by pH. These effects were prominent in Acidobacteria, while Actinobacteria and Gammaroteobacteria communities were affected by original and bioavailable copper. Reproduction and survival of the collembolan F. candida was not affected by the studied copper concentrations. However, the transcriptomic responses to copper reflected a mechanism of copper transport and detoxification, while pH exerted effects on nucleotide and protein metabolism and (acute) inflammatory response. We conclude that microbial community structure reflected the history of copper contamination, while gene expression analysis of F. candida is associated with the current level of bioavailable copper. The study is a first step in the development of a molecular strategy aiming at a more comprehensive assessment of various aspects of soil quality and ecotoxicology.

  17. Fabrication of eco-friendly PNP transistor using RF magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Kumar, B. Santhosh; Harinee, N.; Purvaja, K.; Shanker, N. Praveen; Manikandan, M.; Aparnadevi, N.; Mukilraj, T.; Venkateswaran, C.

    2018-05-01

    An effort has been made to fabricate a thin film transistor using eco-friendly oxide semiconductor materials. Oxide semiconductor materials are cost - effective, thermally and chemically stable with high electron/hole mobility. Copper (II) oxide is a p-type semiconductor and zinc oxide is an n-type semiconductor. A pnp thin film transistor was fabricated using RF magnetron sputtering. The films deposited have been subjected to structural characterization using AFM. I-V characterization of the fabricated device, Ag/CuO/ZnO/CuO/Ag, confirms transistor behaviour. The mechanism of electron/hole transport of the device is discussed below.

  18. 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.

  19. Room-temperature synthesized copper iodide thin film as degenerate p-type transparent conductor with a boosted figure of merit

    PubMed Central

    Kneiβ, Max; Lorenz, Michael

    2016-01-01

    A degenerate p-type conduction of cuprous iodide (CuI) thin films is achieved at the iodine-rich growth condition, allowing for the record high room-temperature conductivity of ∼156 S/cm for as-deposited CuI and ∼283 S/cm for I-doped CuI. At the same time, the films appear clear and exhibit a high transmission of 60–85% in the visible spectral range. The realization of such simultaneously high conductivity and transparency boosts the figure of merit of a p-type TC: its value jumps from ∼200 to ∼17,000 MΩ−1. Polycrystalline CuI thin films were deposited at room temperature by reactive sputtering. Their electrical and optical properties are examined relative to other p-type transparent conductors. The transport properties of CuI thin films were investigated by temperature-dependent conductivity measurements, which reveal a semiconductor–metal transition depending on the iodine/argon ratio in the sputtering gas. PMID:27807139

  20. A 37-year-old Menkes disease patient-Residual ATP7A activity and early copper administration as key factors in beneficial treatment.

    PubMed

    Tümer, Z; Petris, M; Zhu, S; Mercer, J; Bukrinski, J; Bilz, S; Baerlocher, K; Horn, N; Møller, L B

    2017-11-01

    Menkes disease (MD) is a lethal disorder characterized by severe neurological symptoms and connective tissue abnormalities; and results from malfunctioning of cuproenzymes, which cannot receive copper due to a defective intracellular copper transporting protein, ATP7A. Early parenteral copper-histidine supplementation may modify disease progression substantially but beneficial effects of long-term treatment have been recorded in only a few patients. Here we report on the eldest surviving MD patient (37 years) receiving early-onset and long-term copper treatment. He has few neurological symptoms without connective tissue disturbances; and a missense ATP7A variant, p.(Pro852Leu), which results in impaired protein trafficking while the copper transport function is spared. These findings suggest that some cuproenzymes maintain their function when sufficient copper is provided to the cells; and underline the importance of early initiated copper treatment, efficiency of which is likely to be dependent on the mutant ATP7A function. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  1. 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.

  2. 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.

  3. Charge transport mechanism in p-type copper ion containing triazine thiolate metallopolymer thin film devices

    NASA Astrophysics Data System (ADS)

    K, Deepak; Roy, Amit; Anjaneyulu, P.; Kandaiah, Sakthivel; Pinjare, Sampatrao L.

    2017-10-01

    The charge transport mechanism in copper ions containing 1,3,5-Triazine-2,4,6-trithiolate (CuTCA) based polymer device in sandwich (Ag/CuTCA/Cu) geometry is studied. The current-voltage (I-V) characteristics of the metallopolymer CuTCA device have shown a transition in the charge transport mechanism from Ohmic to Space-charge limited conduction when temperature and voltage are varied. The carriers in CuTCA devices exhibit hopping transport, in which carriers hop from one site to the other. The hole mobility in this polymer device is found to be dependent on electric field E ( μpα√{E } ) and temperature, which suggests that the polymer has inherent disorder. The electric-field coefficient γ and zero-field mobility μ0 are temperature dependent. The values of mobility and activation energies are estimated from temperature (90-140 K) dependent charge transport studies and found to be in the range of 1 × 10-11-8 × 10-12 m2/(V s) and 16.5 meV, respectively. Temperature dependent electric-field coefficient γ is in the order of 17.8 × 10-4 (m/V)1/2, and the value of zero-field mobility μ0 is in the order of 1.2 × 10-11 m2/(V s) at 140 K. A constant phase element (Q) is used to model the device parameters, which are extracted using the Impedance spectroscopy technique. The bandgap of the polymer is estimated to be 2.6 eV from UV-Vis reflectance spectra.

  4. 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.

  5. 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

  6. 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.

  7. Copper Transporter ATP7A Protects Against Endothelial Dysfunction in Type 1 Diabetic Mice by Regulating Extracellular Superoxide Dismutase

    PubMed Central

    Sudhahar, Varadarajan; Urao, Norifumi; Oshikawa, Jin; McKinney, Ronald D.; Llanos, Roxana M.; Mercer, Julian F.B.; Ushio-Fukai, Masuko; Fukai, Tohru

    2013-01-01

    Oxidative stress and endothelial dysfunction contribute to vascular complication in diabetes. Extracellular superoxide dismutase (SOD3) is one of the key antioxidant enzymes that obtains copper via copper transporter ATP7A. SOD3 is secreted from vascular smooth muscles cells (VSMCs) and anchors at the endothelial surface. The role of SOD3 and ATP7A in endothelial dysfunction in type 1 diabetes mellitus (T1DM) is entirely unknown. Here we show that the specific activity of SOD3, but not SOD1, is decreased, which is associated with increased O2•− production in aortas of streptozotocin-induced and genetically induced Ins2Akita T1DM mice. Exogenous copper partially rescued SOD3 activity in isolated T1DM vessels. Functionally, acetylcholine-induced, endothelium-dependent relaxation is impaired in T1DM mesenteric arteries, which is rescued by SOD mimetic tempol or gene transfer of SOD3. Mechanistically, ATP7A expression in T1DM vessels is dramatically decreased whereas other copper transport proteins are not altered. T1DM-induced endothelial dysfunction and decrease of SOD3 activity are rescued in transgenic mice overexpressing ATP7A. Furthermore, SOD3-deficient T1DM mice or ATP7A mutant T1DM mice augment endothelial dysfunction and vascular O2•− production versus T1DM mice. These effects are in part due to hypoinsulinemia in T1DM mice, since insulin treatment, but not high glucose, increases ATP7A expression in VSMCs and restores SOD3 activity in the organoid culture of T1DM vessels. In summary, a decrease in ATP7A protein expression contributes to impaired SOD3 activity, resulting in O2•− overproduction and endothelial dysfunction in blood vessels of T1DM. Thus, restoring copper transporter function is an essential therapeutic approach for oxidant stress–dependent vascular and metabolic diseases. PMID:23884884

  8. Arabidopsis copper transport protein COPT2 participates in the cross talk between iron deficiency responses and low-phosphate signaling.

    PubMed

    Perea-García, Ana; Garcia-Molina, Antoni; Andrés-Colás, Nuria; Vera-Sirera, Francisco; Pérez-Amador, Miguel A; Puig, Sergi; Peñarrubia, Lola

    2013-05-01

    Copper and iron are essential micronutrients for most living organisms because they participate as cofactors in biological processes, including respiration, photosynthesis, and oxidative stress protection. In many eukaryotic organisms, including yeast (Saccharomyces cerevisiae) and mammals, copper and iron homeostases are highly interconnected; yet, such interdependence is not well established in higher plants. Here, we propose that COPT2, a high-affinity copper transport protein, functions under copper and iron deficiencies in Arabidopsis (Arabidopsis thaliana). COPT2 is a plasma membrane protein that functions in copper acquisition and distribution. Characterization of the COPT2 expression pattern indicates a synergic response to copper and iron limitation in roots. We characterized a knockout of COPT2, copt2-1, that leads to increased resistance to simultaneous copper and iron deficiencies, measured as reduced leaf chlorosis and improved maintenance of the photosynthetic apparatus. We propose that COPT2 could play a dual role under iron deficiency. First, COPT2 participates in the attenuation of copper deficiency responses driven by iron limitation, possibly to minimize further iron consumption. Second, global expression analyses of copt2-1 versus wild-type Arabidopsis plants indicate that low-phosphate responses increase in the mutant. These results open up new biotechnological approaches to fight iron deficiency in crops.

  9. Clusterin (Apolipoprotein J), a Molecular Chaperone That Facilitates Degradation of the Copper-ATPases ATP7A and ATP7B*

    PubMed Central

    Materia, Stephanie; Cater, Michael A.; Klomp, Leo W. J.; Mercer, Julian F. B.; La Fontaine, Sharon

    2011-01-01

    The copper-transporting P1B-type ATPases (Cu-ATPases) ATP7A and ATP7B are key regulators of physiological copper levels. They function to maintain intracellular copper homeostasis by delivering copper to secretory compartments and by trafficking toward the cell periphery to export excess copper. Mutations in the genes encoding ATP7A and ATP7B lead to copper deficiency and toxicity disorders, Menkes and Wilson diseases, respectively. This report describes the interaction between the Cu-ATPases and clusterin and demonstrates a chaperone-like role for clusterin in facilitating their degradation. Clusterin interacted with both ATP7A and ATP7B in mammalian cells. This interaction increased under conditions of oxidative stress and with mutations in ATP7B that led to its misfolding and mislocalization. A Wilson disease patient mutation (G85V) led to enhanced ATP7B turnover, which was further exacerbated when cells overexpressed clusterin. We demonstrated that clusterin-facilitated degradation of mutant ATP7B is likely to involve the lysosomal pathway. The knockdown and overexpression of clusterin increased and decreased, respectively, the Cu-ATPase-mediated copper export capacity of cells. These results highlight a new role for intracellular clusterin in mediating Cu-ATPase quality control and hence in the normal maintenance of copper homeostasis, and in promoting cell survival in the context of disease. Based on our findings, it is possible that variations in clusterin expression and function could contribute to the variable clinical expression of Menkes and Wilson diseases. PMID:21242307

  10. Increased iron supplied through Fet3p results in replicative life span extension of Saccharomyces cerevisiae under conditions requiring respiratory metabolism.

    PubMed

    Botta, Gabriela; Turn, Christina S; Quintyne, Nicholas J; Kirchman, Paul A

    2011-10-01

    We have previously shown that copper supplementation extends the replicative life span of Saccharomyces cerevisiae when grown under conditions forcing cells to respire. We now show that copper's effect on life span is through Fet3p, a copper containing enzyme responsible for high affinity transport of iron into yeast cells. Life span extensions can also be obtained by supplementing the growth medium with 1mM ferric chloride. Extension by high iron levels is still dependent on the presence of Fet3p. Life span extension by iron or copper requires growth on media containing glycerol as the sole carbon source, which forces yeast to respire. Yeast grown on glucose containing media supplemented with iron show no extension of life span. The iron associated with cells grown in media supplemented with copper or iron is 1.4-1.8 times that of cells grown without copper or iron supplementation. As with copper supplementation, iron supplementation partially rescues the life span of superoxide dismutase mutants. Cells grown with copper supplementation display decreased production of superoxide as measured by dihydroethidium staining. Copyright © 2011 Elsevier Inc. All rights reserved.

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

    Rettie, Alexander J. E.; Sturza, Mihai; Malliakas, Christos D.

    The two-dimensional material KCu 3–xSe 2 was synthesized using both a K 2Se 3 flux and directly from the elements. It crystallizes in the CsAg 3S 2 structure (monoclinic space group C2/m with a = 15.417(3) Å, b = 4.0742(8) Å, c = 8.3190(17) Å, and β = 112.94(3)°), and single-crystal refinement revealed infinite copper-deficient [Cu 3–xSe 2]– layers separated by K + ions. Thermal analysis indicated that KCu 3–xSe 2 melts congruently at ~755 °C. UV–vis spectroscopy showed an optical band gap of ~1.35 eV that is direct in nature, as confirmed by electronic structure calculations. Electronic transport measurementsmore » on single crystals yielded an in-plane resistivity of ~6 × 10 –1 Ω cm at 300 K that has a complex temperature dependence. The results of Seebeck coefficient measurements were consistent with a doped p-type semiconductor (S = +214 μV K –1 at 300 K), with doping being attributed to copper vacancies. Transport is dominated by low-mobility (on the order of 1 cm 2 V –1 s –1) holes caused by relatively flat valence bands with substantial Cu 3d character and a significant concentration of Cu ion vacancy defects (p ~ 10 19 cm –3) in this material. In conclusion, electronic band structure calculations showed that electrons should be significantly more mobile in this structure type.« less

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Effects of impurities in biodiesel-derived glycerol on growth and expression of heavy metal ion homeostasis genes and gene products in Pseudomonas putida LS46.

    PubMed

    Fu, Jilagamazhi; Sharma, Parveen; Spicer, Vic; Krokhin, Oleg V; Zhang, Xiangli; Fristensky, Brian; Wilkins, John A; Cicek, Nazim; Sparling, Richard; Levin, David B

    2015-07-01

    Biodiesel production-derived waste glycerol (WG) was previously investigated as potential carbon source for medium chain length polyhydroxyalkanoate (mcl-PHA) production by Pseudomonas putida LS46. In this study, we evaluated the effect of impurities in the WG on P. putida LS46 physiology during exponential growth and corresponding changes in transcription and protein expression profiles compared with cells grown on pure, reagent grade glycerol. High concentration of metal ions, such as Na(+), and numbers of heavy metals ion, such as copper, ion, zinc, were detected in biodiesel-derived WG. Omics analysis from the corresponding cultures suggested altered expression of genes involved in transport and metabolism of ammonia and heavy metal ions. Expression of three groups of heavy metal homeostasis genes was significantly changed (mostly upregulated) in WG cultures and included the following: copper-responded cluster 1 and 2 genes, primarily containing cusABC; two copies of copAB and heavy metal translocating P-type ATPase; Fur-regulated, TonB-dependent siderophore receptor; and several cobalt/zinc/cadmium transporters. Expression of these genes suggests regulation of intracellular concentrations of heavy metals during growth on biodiesel-derived glycerol. Finally, a number of genes involved in adapting to, or metabolizing free fatty acids and other nonheavy metal contaminants, such as Na(+), were also upregulated in P. putida LS46 grown on biodiesel-derived glycerol.

  17. 49 CFR 192.279 - Copper pipe.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 3 2011-10-01 2011-10-01 false Copper pipe. 192.279 Section 192.279 Transportation Other Regulations Relating to Transportation (Continued) PIPELINE AND HAZARDOUS MATERIALS SAFETY... Copper pipe. Copper pipe may not be threaded except that copper pipe used for joining screw fittings or...

  18. Mechanisms of charge transfer in human copper ATPases ATP7A and ATP7B.

    PubMed

    Tadini-Buoninsegni, Francesco; Smeazzetto, Serena

    2017-04-01

    ATP7A and ATP7B are Cu + -transporting ATPases of subclass IB and play a fundamental role in intracellular copper homeostasis. ATP7A/B transfer Cu + ions across the membrane from delivery to acceptor proteins without establishing a free Cu + gradient. Transfer of copper across the membrane is coupled to ATP hydrolysis. Current measurements on solid supported membranes (SSM) were performed to investigate the mechanism of copper-related charge transfer across ATP7A and ATP7B. SSM measurements demonstrated that electrogenic copper displacement occurs within ATP7A/B following addition of ATP and formation of the phosphorylated intermediate. Comparison of the time constants for cation displacement in ATP7A/B and sarcoplasmic reticulum Ca 2+ -ATPase is consistent with the slower phosphoenzyme formation in copper ATPases. Moreover, ATP-dependent copper transfer in ATP7A/B is not affected by varying the pH, suggesting that net proton counter-transport may not occur in copper ATPases. Platinum anticancer drugs activate ATP7A/B and are subjected to ATP-dependent vectorial displacement with a mechanism analogous to that of copper. © 2016 IUBMB Life, 69(4):218-225, 2017. © 2017 International Union of Biochemistry and Molecular Biology.

  19. 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.

  20. 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.

  1. Arabidopsis Copper Transport Protein COPT2 Participates in the Cross Talk between Iron Deficiency Responses and Low-Phosphate Signaling1[C][W

    PubMed Central

    Perea-García, Ana; Garcia-Molina, Antoni; Andrés-Colás, Nuria; Vera-Sirera, Francisco; Pérez-Amador, Miguel A.; Puig, Sergi; Peñarrubia, Lola

    2013-01-01

    Copper and iron are essential micronutrients for most living organisms because they participate as cofactors in biological processes, including respiration, photosynthesis, and oxidative stress protection. In many eukaryotic organisms, including yeast (Saccharomyces cerevisiae) and mammals, copper and iron homeostases are highly interconnected; yet, such interdependence is not well established in higher plants. Here, we propose that COPT2, a high-affinity copper transport protein, functions under copper and iron deficiencies in Arabidopsis (Arabidopsis thaliana). COPT2 is a plasma membrane protein that functions in copper acquisition and distribution. Characterization of the COPT2 expression pattern indicates a synergic response to copper and iron limitation in roots. We characterized a knockout of COPT2, copt2-1, that leads to increased resistance to simultaneous copper and iron deficiencies, measured as reduced leaf chlorosis and improved maintenance of the photosynthetic apparatus. We propose that COPT2 could play a dual role under iron deficiency. First, COPT2 participates in the attenuation of copper deficiency responses driven by iron limitation, possibly to minimize further iron consumption. Second, global expression analyses of copt2-1 versus wild-type Arabidopsis plants indicate that low-phosphate responses increase in the mutant. These results open up new biotechnological approaches to fight iron deficiency in crops. PMID:23487432

  2. 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.

  3. Study on dioxygen reduction by mutational modifications of the hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase

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

    Morishita, Hirotoshi; Kurita, Daisuke; Kataoka, Kunishige

    2014-07-18

    Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The singlemore » turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase.« less

  4. Copper homeostasis in grapevine: functional characterization of the Vitis vinifera copper transporter 1.

    PubMed

    Martins, Viviana; Bassil, Elias; Hanana, Mohsen; Blumwald, Eduardo; Gerós, Hernâni

    2014-07-01

    The Vitis vinifera copper transporter 1 is capable of self-interaction and mediates intracellular copper transport. An understanding of copper homeostasis in grapevine (Vitis vinifera L.) is particularly relevant to viticulture in which copper-based fungicides are intensively used. In the present study, the Vitis vinifera copper transporter 1 (VvCTr1), belonging to the Ctr family of copper transporters, was cloned and functionally characterized. Amino acid sequence analysis showed that VvCTr1 monomers are small peptides composed of 148 amino acids with 3 transmembrane domains and several amino acid residues typical of Ctr transporters. Bimolecular fluorescence complementation (BiFC) demonstrated that Ctr monomers are self-interacting and subcellular localization studies revealed that VvCTr1 is mobilized via the trans-Golgi network, through the pre-vacuolar compartment and located to the vacuolar membrane. The heterologous expression of VvCTr1 in a yeast strain lacking all Ctr transporters fully rescued the phenotype, while a deficient complementation was observed in a strain lacking only plasma membrane-bound Ctrs. Given the common subcellular localization of VvCTr1 and AtCOPT5 and the highest amino acid sequence similarity in comparison to the remaining AtCOPT proteins, Arabidopsis copt5 plants were stably transformed with VvCTr1. The impairment in root growth observed in copt5 seedlings in copper-deficient conditions was fully rescued by VvCTr1, further supporting its involvement in intracellular copper transport. Expression studies in V. vinifera showed that VvCTr1 is mostly expressed in the root system, but transcripts were also present in leaves and stems. The functional characterization of VvCTr-mediated copper transport provides the first step towards understanding the physiological and molecular responses of grapevines to copper-based fungicides.

  5. Impact of copper ligand mutations on a cupredoxin with a green copper center.

    PubMed

    Roger, Magali; Sciara, Giuliano; Biaso, Frédéric; Lojou, Elisabeth; Wang, Xie; Bauzan, Marielle; Giudici-Orticoni, Marie-Thérèse; Vila, Alejandro J; Ilbert, Marianne

    2017-05-01

    Mononuclear cupredoxins contain a type 1 copper center with a trigonal or tetragonal geometry usually maintained by four ligands, a cystein, two histidines and a methionine. The recent discovery of new members of this family with unusual properties demonstrates, however, the versatility of this class of proteins. Changes in their ligand set lead to drastic variation in their metal site geometry and in the resulting spectroscopic and redox features. In our work, we report the identification of the copper ligands in the recently discovered cupredoxin AcoP. We show that even though AcoP possesses a classical copper ligand set, it has a highly perturbed copper center. In depth studies of mutant's properties suggest a high degree of constraint existing in the copper center of the wild type protein and even the addition of exogenous ligands does not lead to the reconstitution of the initial copper center. Not only the chemical nature of the axial ligand but also constraints brought by its covalent binding to the protein backbone might be critical to maintain a green copper site with high redox potential. This work illustrates the importance of experimentally dissecting the molecular diversity of cupredoxins to determine the molecular determinants responsible for their copper center geometry and redox potential. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. 49 CFR 192.377 - Service lines: Copper.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 3 2011-10-01 2011-10-01 false Service lines: Copper. 192.377 Section 192.377 Transportation Other Regulations Relating to Transportation (Continued) PIPELINE AND HAZARDOUS MATERIALS SAFETY... § 192.377 Service lines: Copper. Each copper service line installed within a building must be protected...

  7. 49 CFR 192.377 - Service lines: Copper.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 3 2010-10-01 2010-10-01 false Service lines: Copper. 192.377 Section 192.377 Transportation Other Regulations Relating to Transportation (Continued) PIPELINE AND HAZARDOUS MATERIALS SAFETY... § 192.377 Service lines: Copper. Each copper service line installed within a building must be protected...

  8. The mammalian phosphate carrier SLC25A3 is a mitochondrial copper transporter required for cytochrome c oxidase biogenesis

    PubMed Central

    Boulet, Aren; Vest, Katherine E.; Maynard, Margaret K.; Gammon, Micah G.; Russell, Antoinette C.; Mathews, Alexander T.; Cole, Shelbie E.; Zhu, Xinyu; Phillips, Casey B.; Kwong, Jennifer Q.; Dodani, Sheel C.; Leary, Scot C.; Cobine, Paul A.

    2018-01-01

    Copper is required for the activity of cytochrome c oxidase (COX), the terminal electron-accepting complex of the mitochondrial respiratory chain. The likely source of copper used for COX biogenesis is a labile pool found in the mitochondrial matrix. In mammals, the proteins that transport copper across the inner mitochondrial membrane remain unknown. We previously reported that the mitochondrial carrier family protein Pic2 in budding yeast is a copper importer. The closest Pic2 ortholog in mammalian cells is the mitochondrial phosphate carrier SLC25A3. Here, to investigate whether SLC25A3 also transports copper, we manipulated its expression in several murine and human cell lines. SLC25A3 knockdown or deletion consistently resulted in an isolated COX deficiency in these cells, and copper addition to the culture medium suppressed these biochemical defects. Consistent with a conserved role for SLC25A3 in copper transport, its heterologous expression in yeast complemented copper-specific defects observed upon deletion of PIC2. Additionally, assays in Lactococcus lactis and in reconstituted liposomes directly demonstrated that SLC25A3 functions as a copper transporter. Taken together, these data indicate that SLC25A3 can transport copper both in vitro and in vivo. PMID:29237729

  9. Periplasmic response upon disruption of transmembrane Cu transport in Pseudomonas aeruginosa.

    PubMed

    Raimunda, Daniel; Padilla-Benavides, Teresita; Vogt, Stefan; Boutigny, Sylvain; Tomkinson, Kaleigh N; Finney, Lydia A; Argüello, José M

    2013-02-01

    Pseudomonas aeruginosa, an opportunistic pathogen, has two transmembrane Cu(+) transport ATPases, CopA1 and CopA2. Both proteins export cytoplasmic Cu(+) into the periplasm and mutation of either gene leads to attenuation of virulence. CopA1 is required for maintaining cytoplasmic copper levels, while CopA2 provides copper for cytochrome c oxidase assembly. We hypothesized that transported Cu(+) ions would be directed to their destination via specific periplasmic partners and disruption of transport should affect the periplasmic copper homeostasis. Supporting this, mutation of either ATPase gene led to large increments in periplasmic cuproprotein levels. Toward identifying the proteins participating in this cellular response the periplasmic metalloproteome was resolved in non-denaturing bidimensional gel electrophoresis, followed by X-ray fluorescence visualization and identification by mass-spectrometry. A single spot containing the electron shuttle protein azurin was responsible for the observed increments in cuproprotein contents. In agreement, lack of either Cu(+)-ATPase induced an increase in azu transcription. This is associated with an increase in the expression of anr and rpoS oxidative stress response regulators, rather than cueR, a copper sensing regulator. We propose that azurin overexpression and accumulation in the periplasm is part of the cellular response to cytoplasmic oxidative stress in P. aeruginosa.

  10. Comparative study on life cycle environmental impact assessment of copper and aluminium cables

    NASA Astrophysics Data System (ADS)

    Bao, Wei; Lin, Ling; Song, Dan; Guo, Huiting; Chen, Liang; Sun, Liang; Liu, Mei; Chen, Jianhua

    2017-11-01

    With the rapid development of industrialization and urbanization in China, domestic demands for copper and aluminium resources increase continuously and the output of copper and aluminium minerals rises steadily. The output of copper in China increased from 0.6 million tons (metal quantity) in 2003 to 1.74 million tons (metal quantity) in 2014, and the output of bauxite increased from 21 million tons in 2006 to 59.21 million tons in 2014. In the meantime, the import of copper and aluminium minerals of China is also on a rise. The import of copper concentrate and bauxite increased from 4.94 million tons and 9.68 million tons in 2006 to 10.08 million tons and 70.75 million tons in 2013 respectively. Copper and aluminium resources are widely applied in fields such as construction, electrical and electronics, machinery manufacturing, and transportation, and serve as important material basis for the national economic and social development of China. Cable industry is a typical industry where copper and aluminium resources are widely used. In this paper, a product assessment model is built from the perspective of product life cycle. Based on CNLCD database, differences in environmental impacts of copper and aluminium cables are analyzed from aspects such as resource acquisition, product production, transportation, utilization, and resource recycling. Furthermore, the advantages and disadvantages of products at different stages with different types of environmental impact are analyzed, so as to provide data support for cable industry in terms of product design and production, etc.

  11. 49 CFR 192.125 - Design of copper pipe.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 3 2011-10-01 2011-10-01 false Design of copper pipe. 192.125 Section 192.125 Transportation Other Regulations Relating to Transportation (Continued) PIPELINE AND HAZARDOUS MATERIALS SAFETY... BY PIPELINE: MINIMUM FEDERAL SAFETY STANDARDS Pipe Design § 192.125 Design of copper pipe. (a) Copper...

  12. Ionophore and Biometal Modulation of P-glycoprotein Expression and Function in Human Brain Microvascular Endothelial Cells.

    PubMed

    McInerney, Mitchell P; Volitakis, Irene; Bush, Ashley I; Banks, William A; Short, Jennifer L; Nicolazzo, Joseph A

    2018-03-05

    Biometals such as zinc and copper have been shown to affect tight junction expression and subsequently blood-brain barrier (BBB) integrity. Whether these biometals also influence the expression and function of BBB transporters such as P-glycoprotein (P-gp) however is currently unknown. Using the immortalised human cerebral microvascular endothelial (hCMEC/D3) cell line, an in-cell western assay (alongside western blotting) assessed relative P-gp expression after treatment with the metal ionophore clioquinol and biometals zinc and copper. The fluorescent P-gp substrate rhodamine-123 was employed to observe functional modulation, and inductively coupled plasma mass spectrometry (ICP-MS) provided information on biometal trafficking. A 24-h treatment with clioquinol, zinc and copper (0.5, 0.5 and 0.1 μM) induced a significant upregulation of P-gp (1.7-fold) assessed by in-cell western and this was confirmed with western blotting (1.8-fold increase). This same treatment resulted in a 23% decrease in rhodamine-123 accumulation over a 1 h incubation. ICP-MS demonstrated that while t8his combination treatment had no effect on intracellular zinc concentrations, the treatment significantly enhanced bioavailable copper (4.6-fold). Enhanced delivery of copper to human brain microvascular endothelial cells is associated with enhanced expression and function of the important efflux pump P-gp, which may provide therapeutic opportunities for P-gp modulation.

  13. Copper Coordination in the Full-Length, Recombinant Prion Protein†

    PubMed Central

    Burns, Colin S.; Aronoff-Spencer, Eliah; Legname, Giuseppe; Prusiner, Stanley B.; Antholine, William E.; Gerfen, Gary J.; Peisach, Jack; Millhauser, Glenn L.

    2010-01-01

    The prion protein (PrP) binds divalent copper at physiologically relevant conditions and is believed to participate in copper regulation or act as a copper-dependent enzyme. Ongoing studies aim at determining the molecular features of the copper binding sites. The emerging consensus is that most copper binds in the octarepeat domain, which is composed of four or more copies of the fundamental sequence PHGGGWGQ. Previous work from our laboratory using PrP-derived peptides, in conjunction with EPR and X-ray crystallography, demonstrated that the HGGGW segment constitutes the fundamental binding unit in the octarepeat domain [Burns et al. (2002) Biochemistry 41, 3991–4001; Aronoff-Spencer et al. (2000) Biochemistry 39, 13760–13771]. Copper coordination arises from the His imidazole and sequential deprotonated glycine amides. In this present work, recombinant, full-length Syrian hamster PrP is investigated using EPR methodologies. Four copper ions are taken up in the octarepeat domain, which supports previous findings. However, quantification studies reveal a fifth binding site in the flexible region between the octarepeats and the PrP globular C-terminal domain. A series of PrP peptide constructs show that this site involves His96 in the PrP(92–96) segment GGGTH. Further examination by X-band EPR, S-band EPR, and electron spin–echo envelope spectroscopy, demonstrates coordination by the His96 imidazole and the glycine preceding the threonine. The copper affinity for this type of binding site is highly pH dependent, and EPR studies here show that recombinant PrP loses its affinity for copper below pH 6.0. These studies seem to provide a complete profile of the copper binding sites in PrP and support the hypothesis that PrP function is related to its ability to bind copper in a pH-dependent fashion. PMID:12779334

  14. Molecular and biochemical characterization of a unique mutation in CCS, the human copper chaperone to superoxide dismutase

    PubMed Central

    Huppke, Peter; Brendel, Cornelia; Korenke, Georg Christoph; Marquardt, Iris; Donsante, Anthony; Yi, Ling; Hicks, Julia D.; Steinbach, Peter J.; Wilson, Callum; Elpeleg, Orly; Møller, Lisbeth Birk; Christodoulou, John; Kaler, Stephen G.; Gärtner, Jutta

    2012-01-01

    Copper is a trace metal that readily gains and donates electrons, a property that renders it desirable as an enzyme cofactor but dangerous as a source of free radicals. To regulate cellular copper metabolism, an elaborate system of chaperones and transporters has evolved, although no human copper chaperone mutations have been described to date. We describe a child from a consanguineous family who inherited a homozygous mutations in the SLC33A1, encoding an acetyl CoA transporter, and in CCS, encoding the copper chaperone for superoxide dismutase. The CCS mutation, p.Arg163Trp, predicts substitution of a highly conserved arginine residue at position 163 with tryptophan in domain II of CCS, which interacts directly with SOD1. Biochemical analyses of the patient’s fibroblasts, mammalian cell transfections, immunoprecipitation assays, and Lys7Δ (CCS homolog) yeast complementation support the pathogenicity of the mutation. Expression of CCS was reduced and binding of CCS to SOD1 impaired. As a result this mutation causes reduced SOD1 activity and may impair other mechanisms important for normal copper homeostasis. CCS-Arg163Trp represents the primary example of a human mutation in a gene coding for a copper chaperone. PMID:22508683

  15. ATP7A-related copper transport diseases-emerging concepts and future trends.

    PubMed

    Kaler, Stephen G

    2011-01-01

    This Review summarizes recent advances in understanding copper-transporting ATPase 1 (ATP7A), and examines the neurological phenotypes associated with dysfunction of this protein. Involvement of ATP7A in axonal outgrowth, synapse integrity and neuronal activation underscores the fundamental importance of copper metabolism to neurological function. Defects in ATP7A cause Menkes disease, an infantile-onset, lethal condition. Neonatal diagnosis and early treatment with copper injections enhance survival in patients with this disease, and can normalize clinical outcomes if mutant ATP7A molecules retain small amounts of residual activity. Gene replacement rescues a mouse model of Menkes disease, suggesting a potential therapeutic approach for patients with complete loss-of-function ATP7A mutations. Remarkably, a newly discovered ATP7A disorder-isolated distal motor neuropathy-has none of the characteristic clinical or biochemical abnormalities of Menkes disease or its milder allelic variant occipital horn syndrome (OHS), instead resembling Charcot-Marie-Tooth disease type 2. These findings indicate that ATP7A has a crucial but previously unappreciated role in motor neuron maintenance, and that the mechanism underlying ATP7A-related distal motor neuropathy is distinct from Menkes disease and OHS pathophysiology. Collectively, these insights refine our knowledge of the neurology of ATP7A-related copper transport diseases and pave the way for further progress in understanding ATP7A function.

  16. ATP7B detoxifies silver in ciliated airway epithelial cells

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

    Ibricevic, Aida, E-mail: aidaibricevic@hotmail.co; Brody, Steven L., E-mail: sbrody@dom.wustl.ed; Youngs, Wiley J., E-mail: youngs@uakron.ed

    2010-03-15

    Silver is a centuries-old antibiotic agent currently used to treat infected burns. The sensitivity of a wide range of drug-resistant microorganisms to silver killing suggests that it may be useful for treating refractory lung infections. Toward this goal, we previously developed a methylated caffeine silver acetate compound, SCC1, that exhibits broad-spectrum antimicrobial activity against clinical strains of bacteria in vitro and when nebulized to lungs in mouse infection models. Preclinical testing of high concentrations of SCC1 in primary culture mouse tracheal epithelial cells (mTEC) showed selective ciliated cell death. Ciliated cell death was induced by both silver- and copper-containing compoundsmore » but not by the methylated caffeine portion of SCC1. We hypothesized that copper transporting P-type ATPases, ATP7A and ATP7B, play a role in silver detoxification in the airway. In mTEC, ATP7A was expressed in non-ciliated cells, whereas ATP7B was expressed only in ciliated cells. The exposure of mTEC to SCC1 induced the trafficking of ATP7B, but not ATP7A, suggesting the presence of a cell-specific silver uptake and detoxification mechanisms. Indeed, the expression of the copper uptake protein CTR1 was also restricted to ciliated cells. A role of ATP7B in silver detoxification was further substantiated when treatment of SCC1 significantly increased cell death in ATP7B shRNA-treated HepG2 cells. In addition, mTEC from ATP7B{sup -/-} mice showed enhanced loss of ciliated cells compared to wild type. These studies are the first to demonstrate a cell type-specific expression of the Ag{sup +}/Cu{sup +} transporters ATP7A, ATP7B, and CTR1 in airway epithelial cells and a role for ATP7B in detoxification of these metals in the lung.« less

  17. Cu/Cu2O nanocomposite films as a p-type modified layer for efficient perovskite solar cells.

    PubMed

    Chen, You-Jyun; Li, Ming-Hsien; Huang, Jung-Chun-Andrew; Chen, Peter

    2018-05-16

    Cu/Cu 2 O films grown by ion beam sputtering were used as p-type modified layers to improve the efficiency and stability of perovskite solar cells (PSCs) with an n-i-p heterojunction structure. The ratio of Cu to Cu 2 O in the films can be tuned by the oxygen flow ratio (O 2 /(O 2  + Ar)) during the sputtering of copper. Auger electron spectroscopy was performed to determine the elemental composition and chemical state of Cu in the films. Ultraviolet photoelectron spectroscopy and photoluminescence spectroscopy revealed that the valence band maximum of the p-type Cu/Cu 2 O matches well with the perovskite. The Cu/Cu 2 O film not only acts as a p-type modified layer but also plays the role of an electron blocking buffer layer. By introducing the p-type Cu/Cu 2 O films between the low-mobility hole transport material, spiro-OMeTAD, and the Ag electrode in the PSCs, the device durability and power conversion efficiency (PCE) were effectively improved as compared to the reference devices without the Cu/Cu 2 O interlayer. The enhanced PCE is mainly attributed to the high hole mobility of the p-type Cu/Cu 2 O film. Additionally, the Cu/Cu 2 O film serves as a protective layer against the penetration of humidity and Ag into the perovskite active layer.

  18. The mammalian phosphate carrier SLC25A3 is a mitochondrial copper transporter required for cytochrome c oxidase biogenesis.

    PubMed

    Boulet, Aren; Vest, Katherine E; Maynard, Margaret K; Gammon, Micah G; Russell, Antoinette C; Mathews, Alexander T; Cole, Shelbie E; Zhu, Xinyu; Phillips, Casey B; Kwong, Jennifer Q; Dodani, Sheel C; Leary, Scot C; Cobine, Paul A

    2018-02-09

    Copper is required for the activity of cytochrome c oxidase (COX), the terminal electron-accepting complex of the mitochondrial respiratory chain. The likely source of copper used for COX biogenesis is a labile pool found in the mitochondrial matrix. In mammals, the proteins that transport copper across the inner mitochondrial membrane remain unknown. We previously reported that the mitochondrial carrier family protein Pic2 in budding yeast is a copper importer. The closest Pic2 ortholog in mammalian cells is the mitochondrial phosphate carrier SLC25A3. Here, to investigate whether SLC25A3 also transports copper, we manipulated its expression in several murine and human cell lines. SLC25A3 knockdown or deletion consistently resulted in an isolated COX deficiency in these cells, and copper addition to the culture medium suppressed these biochemical defects. Consistent with a conserved role for SLC25A3 in copper transport, its heterologous expression in yeast complemented copper-specific defects observed upon deletion of PIC2 Additionally, assays in Lactococcus lactis and in reconstituted liposomes directly demonstrated that SLC25A3 functions as a copper transporter. Taken together, these data indicate that SLC25A3 can transport copper both in vitro and in vivo . © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

  19. Copper transporters and chaperones CTR1, CTR2, ATOX1, and CCS as determinants of cisplatin sensitivity.

    PubMed

    Bompiani, Kristin M; Tsai, Cheng-Yu; Achatz, Felix P; Liebig, Janika K; Howell, Stephen B

    2016-09-01

    The development of resistance to cisplatin (cDDP) is commonly accompanied by reduced drug uptake or increased efflux. Previous studies in yeast and murine embryonic fibroblasts have reported that the copper (Cu) transporters and chaperones participate in the uptake, efflux, and intracellular distribution of cDDP. However, there is conflicting data from studies in human cells. We used CRISPR-Cas9 genome editing to individually knock out the human copper transporters CTR1 and CTR2 and the copper chaperones ATOX1 and CCS. Isogenic knockout cell lines were generated in both human HEK-293T and ovarian carcinoma OVCAR8 cells. All knockout cell lines had slowed growth compared to parental cells, small changes in basal Cu levels, and varying sensitivities to Cu depending on the gene targeted. However, all of the knockouts demonstrated only modest 2 to 5-fold changes in cDDP sensitivity that did not differ from the range of sensitivities of 10 wild type clones grown from the same parental cell population. We conclude that, under basal conditions, loss of CTR1, CTR2, ATOX1, or CCS does not produce a change in cisplatin sensitivity that exceeds the variance found within the parental population, suggesting that they are not essential to the mechanism by which cDDP enters these cell lines and is transported to the nucleus.

  20. Copper attachment to a non-octarepeat site in prion protein

    NASA Astrophysics Data System (ADS)

    Hodak, Miroslav; Bernholc, Jerry

    2010-03-01

    Prion protein, PrP, plays a causative role in several neurodegenerative diseases, including mad cow disease in cattle and Creutzfeldt-Jakob disease in humans. The PrP is known to efficiently bind copper ions and this ability has been linked to its function. PrP contains up to six binding sites, four of which are located in the so-called octarepeat region and are now well known. The binding sites outside this region are still largely undetermined, despite evidence of their relevance to prion diseases. Using a hybrid DFT/DFT, which combines Kohn-Sham DFT with orbital-free DFT to achieve accurate and efficient description of solvent effects in ab initio calculations, we have investigated copper attachment to the sequence GGGTH, which represents the copper binding site located at His96. We have considered both NNNN and NNNO types of copper coordination, as suggested by experiments. Our calculations have determined the geometry of copper attachment site and its energetics. Comparison to the already known binding sites provides insight into the process of copper uptake in PrP.

  1. A Role for the ATP7A Copper-transporting ATPase in Macrophage Bactericidal Activity*

    PubMed Central

    White, Carine; Lee, Jaekwon; Kambe, Taiho; Fritsche, Kevin; Petris, Michael J.

    2009-01-01

    Copper is an essential micronutrient that is necessary for healthy immune function. This requirement is underscored by an increased susceptibility to bacterial infection in copper-deficient animals; however, a molecular understanding of its importance in immune defense is unknown. In this study, we investigated the effect of proinflammatory agents on copper homeostasis in RAW264.7 macrophages. Interferon-γ was found to increase expression of the high affinity copper importer, CTR1, and stimulate copper uptake. This was accompanied by copper-stimulated trafficking of the ATP7A copper exporter from the Golgi to vesicles that partially overlapped with phagosomal compartments. Silencing of ATP7A expression attenuated bacterial killing, suggesting a role for ATP7A-dependent copper transport in the bactericidal activity of macrophages. Significantly, a copper-sensitive mutant of Escherichia coli lacking the CopA copper-transporting ATPase was hypersensitive to killing by RAW264.7 macrophages, and this phenotype was dependent on ATP7A expression. Collectively, these data suggest that copper-transporting ATPases, CopA and ATP7A, in both bacteria and macrophage are unique determinants of bacteria survival and identify an unexpected role for copper at the host-pathogen interface. PMID:19808669

  2. Triplin, a small molecule, reveals copper ion transport in ethylene signaling from ATX1 to RAN1.

    PubMed

    Li, Wenbo; Lacey, Randy F; Ye, Yajin; Lu, Juan; Yeh, Kuo-Chen; Xiao, Youli; Li, Laigeng; Wen, Chi-Kuang; Binder, Brad M; Zhao, Yang

    2017-04-01

    Copper ions play an important role in ethylene receptor biogenesis and proper function. The copper transporter RESPONSIVE-TO-ANTAGONIST1 (RAN1) is essential for copper ion transport in Arabidopsis thaliana. However it is still unclear how copper ions are delivered to RAN1 and how copper ions affect ethylene receptors. There is not a specific copper chelator which could be used to explore these questions. Here, by chemical genetics, we identified a novel small molecule, triplin, which could cause a triple response phenotype on dark-grown Arabidopsis seedlings through ethylene signaling pathway. ran1-1 and ran1-2 are hypersensitive to triplin. Adding copper ions in growth medium could partially restore the phenotype on plant caused by triplin. Mass spectrometry analysis showed that triplin could bind copper ion. Compared to the known chelators, triplin acts more specifically to copper ion and it suppresses the toxic effects of excess copper ions on plant root growth. We further showed that mutants of ANTIOXIDANT PROTEIN1 (ATX1) are hypersensitive to tiplin, but with less sensitivity comparing with the ones of ran1-1 and ran1-2. Our study provided genetic evidence for the first time that, copper ions necessary for ethylene receptor biogenesis and signaling are transported from ATX1 to RAN1. Considering that triplin could chelate copper ions in Arabidopsis, and copper ions are essential for plant and animal, we believe that, triplin not only could be useful for studying copper ion transport of plants, but also could be useful for copper metabolism study in animal and human.

  3. 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.

  4. 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.

  5. Copper transport and regulation in Schizosaccharomyces pombe

    PubMed Central

    Beaudoin, Jude; Ekici, Seda; Daldal, Fevzi; Ait-Mohand, Samia; Guérin, Brigitte; Labbé, Simon

    2016-01-01

    The fission yeast Schizosaccharomyces pombe has been successfully used as a model to gain fundamental knowledge in understanding how eukaryotic cells acquire copper during vegetative growth. These studies have revealed the existence of a heteromeric Ctr4–Ctr5 plasma membrane complex that mediates uptake of copper within the cells. Furthermore, additional studies have led to the identification of one of the first vacuolar copper transporters, Ctr6, as well as the copper-responsive Cuf1 transcription factor. Recent investigations have extended the use of S. pombe to elucidate new roles for copper metabolism in meiotic differentiation. For example, these studies have led to the discovery of Mfc1, which turned out to be the first example of a meiosis-specific copper transporter. Whereas copper-dependent transcriptional regulation of the Ctr family members is under the control of Cuf1 during mitosis or meiosis, meiosis-specific copper transporter Mfc1 is regulated by the recently discovered transactivator Mca1. It is foreseeable that identification of novel meiotic copper-related proteins will serve as stepping stones to unravel fundamental aspects of copper homoeostasis. PMID:24256274

  6. Copper transport and regulation in Schizosaccharomyces pombe.

    PubMed

    Beaudoin, Jude; Ekici, Seda; Daldal, Fevzi; Ait-Mohand, Samia; Guérin, Brigitte; Labbé, Simon

    2013-12-01

    The fission yeast Schizosaccharomyces pombe has been successfully used as a model to gain fundamental knowledge in understanding how eukaryotic cells acquire copper during vegetative growth. These studies have revealed the existence of a heteromeric Ctr4-Ctr5 plasma membrane complex that mediates uptake of copper within the cells. Furthermore, additional studies have led to the identification of one of the first vacuolar copper transporters, Ctr6, as well as the copper-responsive Cuf1 transcription factor. Recent investigations have extended the use of S. pombe to elucidate new roles for copper metabolism in meiotic differentiation. For example, these studies have led to the discovery of Mfc1, which turned out to be the first example of a meiosis-specific copper transporter. Whereas copper-dependent transcriptional regulation of the Ctr family members is under the control of Cuf1 during mitosis or meiosis, meiosis-specific copper transporter Mfc1 is regulated by the recently discovered transactivator Mca1. It is foreseeable that identification of novel meiotic copper-related proteins will serve as stepping stones to unravel fundamental aspects of copper homoeostasis.

  7. Copper tolerance of the thermoacidophilic archaeon Sulfolobus metallicus: possible role of polyphosphate metabolism.

    PubMed

    Remonsellez, Francisco; Orell, Alvaro; Jerez, Carlos A

    2006-01-01

    It has been postulated that inorganic polyphosphate (polyP) and transport of metal-phosphate complexes could participate in heavy metal tolerance in some bacteria. To study if such a system exists in archaea, the presence of polyP was determined by the electron energy loss spectroscopy (EELS) procedure and quantified by using specific enzymic methods in Sulfolobus acidocaldarius, Sulfolobus metallicus and Sulfolobus solfataricus. All three micro-organisms synthesized polyP during growth, but only S. metallicus greatly accumulated polyP granules. The differences in the capacity to accumulate polyP between these archaea may reflect adaptive responses to their natural environment. Thus, S. metallicus could grow in and tolerate up to 200 mM copper sulfate, with a concomitant decrease in its polyP levels with increasing copper concentrations. On the other hand, S. solfataricus could not grow in or tolerate more than 1-5 mM copper sulfate, most likely due to its low levels of polyP. Shifting S. metallicus cells to copper sulfate concentrations up to 100 mM led to a rapid increase in their exopolyphosphatase (PPX) activity which was concomitant in time with a decrease in their polyP levels and a stimulation of phosphate efflux. Furthermore, copper in the range of 10 microM greatly stimulated PPX activity in cell-free extracts from S. metallicus. The results strongly suggest that a metal tolerance mechanism mediated through polyP is functional in members of the genus Sulfolobus. This ability to accumulate and hydrolyse polyP may play an important role not only in the survival of these micro-organisms in sulfidic mineral environments containing high toxic metals concentrations, but also in their applications in biomining.

  8. 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.

  9. Clusterin and COMMD1 Independently Regulate Degradation of the Mammalian Copper ATPases ATP7A and ATP7B*

    PubMed Central

    Materia, Stephanie; Cater, Michael A.; Klomp, Leo W. J.; Mercer, Julian F. B.; La Fontaine, Sharon

    2012-01-01

    ATP7A and ATP7B are copper-transporting P1B-type ATPases (Cu-ATPases) that are critical for regulating intracellular copper homeostasis. Mutations in the genes encoding ATP7A and ATP7B lead to copper deficiency and copper toxicity disorders, Menkes and Wilson diseases, respectively. Clusterin and COMMD1 were previously identified as interacting partners of these Cu-ATPases. In this study, we confirmed that clusterin and COMMD1 interact to down-regulate both ATP7A and ATP7B. Overexpression and knockdown of clusterin/COMMD1 decreased and increased, respectively, endogenous levels of ATP7A and ATP7B, consistent with a role in facilitating Cu-ATPase degradation. We demonstrate that whereas the clusterin/ATP7B interaction was enhanced by oxidative stress or mutation of ATP7B, the COMMD1/ATP7B interaction did not change under oxidative stress conditions, and only increased with ATP7B mutations that led to its misfolding. Clusterin and COMMD1 facilitated the degradation of ATP7B containing the same Wilson disease-causing C-terminal mutations via different degradation pathways, clusterin via the lysosomal pathway and COMMD1 via the proteasomal pathway. Furthermore, endogenous ATP7B existed in a complex with clusterin and COMMD1, but these interactions were neither competitive nor cooperative and occurred independently of each other. Together these data indicate that clusterin and COMMD1 represent alternative and independent systems regulating Cu-ATPase quality control, and consequently contributing to the maintenance of copper homeostasis. PMID:22130675

  10. Facilitated transport of copper with hydroxyapatite nanoparticles in saturated sand

    USDA-ARS?s Scientific Manuscript database

    Saturated packed column experiments were conducted to investigate the facilitated transport of Cu with hydroxyapatite nanoparticles (nHAP) at different pore water velocities (0.22-2.2 cm min–1), solution pH (6.2-9.0), and fraction of Fe oxide coating on grain surfaces (', 0-0.36). The facilitated tr...

  11. Triplin, a small molecule, reveals copper ion transport in ethylene signaling from ATX1 to RAN1

    PubMed Central

    Li, Wenbo; Ye, Yajin; Lu, Juan; Yeh, Kuo-Chen; Xiao, Youli; Li, Laigeng; Binder, Brad M.

    2017-01-01

    Copper ions play an important role in ethylene receptor biogenesis and proper function. The copper transporter RESPONSIVE-TO-ANTAGONIST1 (RAN1) is essential for copper ion transport in Arabidopsis thaliana. However it is still unclear how copper ions are delivered to RAN1 and how copper ions affect ethylene receptors. There is not a specific copper chelator which could be used to explore these questions. Here, by chemical genetics, we identified a novel small molecule, triplin, which could cause a triple response phenotype on dark-grown Arabidopsis seedlings through ethylene signaling pathway. ran1-1 and ran1-2 are hypersensitive to triplin. Adding copper ions in growth medium could partially restore the phenotype on plant caused by triplin. Mass spectrometry analysis showed that triplin could bind copper ion. Compared to the known chelators, triplin acts more specifically to copper ion and it suppresses the toxic effects of excess copper ions on plant root growth. We further showed that mutants of ANTIOXIDANT PROTEIN1 (ATX1) are hypersensitive to tiplin, but with less sensitivity comparing with the ones of ran1-1 and ran1-2. Our study provided genetic evidence for the first time that, copper ions necessary for ethylene receptor biogenesis and signaling are transported from ATX1 to RAN1. Considering that triplin could chelate copper ions in Arabidopsis, and copper ions are essential for plant and animal, we believe that, triplin not only could be useful for studying copper ion transport of plants, but also could be useful for copper metabolism study in animal and human. PMID:28388654

  12. SLC31 (CTR) Family of Copper Transporters in Health and Disease

    PubMed Central

    Kim, Heejeong; Wu, Xiaobin; Lee, Jaekwon

    2012-01-01

    Copper is a vital mineral for many organisms, yet it is highly toxic as demonstrated by serious health concerns associated with its deficiency or excess accumulation. The SLC31 (CTR) family of copper transporters is a major gateway of copper acquisition in eukaryotes, ranging from yeast to humans. Characterization of the function, modes of action, and regulation of CTR and other molecular factors that functionally cooperate with CTR for copper transport, compartmentalization, incorporation into cuproproteins, and detoxification has revealed that organisms have evolved fascinating mechanisms for tight control of copper metabolism. This research progress further indicates the significance of copper in health and disease and opens avenues for therapeutic control of copper bioavailability and its metabolic pathways. PMID:23506889

  13. The copper rush of the nineties.

    PubMed

    Solioz, Marc

    2016-09-01

    The nineties witnessed the discovery of the copper ATPases, enzymes which transport copper across the cytoplasmic membranes of bacteria and eukaryotes. In the same decade, several other key components of copper homeostasis have also been discovered, like copper chaperones and plasma membrane copper transporters. This has finally led to a molecular understanding of two inherited human diseases related to copper: Menkes disease, manifested by systemic copper deficiency, and Wilson disease, caused by defective secretion of excess copper. A historic perspective and untold stories of the events leading up to these discoveries are presented here.

  14. 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.

  15. Rate and Regulation of Copper Transport by Human Copper Transporter 1 (hCTR1)*

    PubMed Central

    Maryon, Edward B.; Molloy, Shannon A.; Ivy, Kristin; Yu, Huijun; Kaplan, Jack H.

    2013-01-01

    Human copper transporter 1 (hCTR1) is a homotrimer of a 190-amino acid monomer having three transmembrane domains believed to form a pore for copper permeation through the plasma membrane. The hCTR1-mediated copper transport mechanism is not well understood, nor has any measurement been made of the rate at which copper ions are transported by hCTR1. In this study, we estimated the rate of copper transport by the hCTR1 trimer in cultured cells using 64Cu uptake assays and quantification of plasma membrane hCTR1. For endogenous hCTR1, we estimated a turnover number of about 10 ions/trimer/s. When overexpressed in HEK293 cells, a second transmembrane domain mutant of hCTR1 (H139R) had a 3-fold higher Km value and a 4-fold higher turnover number than WT. Truncations of the intracellular C-terminal tail and an AAA substitution of the putative metal-binding HCH C-terminal tripeptide (thought to be required for transport) also exhibited elevated transport rates and Km values when compared with WT hCTR1. Unlike WT hCTR1, H139R and the C-terminal mutants did not undergo regulatory endocytosis in elevated copper. hCTR1 mutants combining methionine substitutions that block transport (M150L,M154L) on the extracellular side of the pore and the high transport H139R or AAA intracellular side mutations exhibited the blocked transport of M150L,M154L, confirming that Cu+ first interacts with the methionines during permeation. Our results show that hCTR1 elements on the intracellular side of the hCTR1 pore, including the carboxyl tail, are not essential for permeation, but serve to regulate the rate of copper entry. PMID:23658018

  16. Calcium- and potassium-permeable plasma membrane transporters are activated by copper in Arabidopsis root tips: linking copper transport with cytosolic hydroxyl radical production.

    PubMed

    Rodrigo-Moreno, Ana; Andrés-Colás, Nuria; Poschenrieder, Charlotte; Gunsé, Benet; Peñarrubia, Lola; Shabala, Sergey

    2013-04-01

    Transition metals such as copper can interact with ascorbate or hydrogen peroxide to form highly reactive hydroxyl radicals (OH(•) ), with numerous implications to membrane transport activity and cell metabolism. So far, such interaction was described for extracellular (apoplastic) space but not cytosol. Here, a range of advanced electrophysiological and imaging techniques were applied to Arabidopsis thaliana plants differing in their copper-transport activity: Col-0, high-affinity copper transporter COPT1-overexpressing (C1(OE) ) seedlings, and T-DNA COPT1 insertion mutant (copt1). Low Cu concentrations (10 µm) stimulated a dose-dependent Gd(3+) and verapamil sensitive net Ca(2+) influx in the root apex but not in mature zone. C1(OE) also showed a fivefold higher Cu-induced K(+) efflux at the root tip level compared with Col-0, and a reduction in basal peroxide accumulation at the root tip after copper exposure. Copper caused membrane disruptions of the root apex in C1(OE) seedlings but not in copt1 plants; this damage was prevented by pretreatment with Gd(3+) . Our results suggest that copper transport into cytosol in root apex results in hydroxyl radical generation at the cytosolic side, with a consequent regulation of plasma membrane OH(•) -sensitive Ca(2+) and K(+) transport systems. © 2012 Blackwell Publishing Ltd.

  17. p.H1069Q mutation in ATP7B and biochemical parameters of copper metabolism and clinical manifestation of Wilson's disease.

    PubMed

    Gromadzka, Graznya; Schmidt, Harmut H J; Genschel, Janine; Bochow, Bettina; Rodo, M; Tarnacka, Beatek; Litwin, Thomas; Chabik, Grzegorz; Członkowska, Anna

    2006-02-01

    We compared the effect of the p.H1069Q mutation and other non-p.H1069Q mutations in ATP7B on the phenotypic expression of Wilson's disease (WD), and assessed whether the clinical phenotype of WD in compound heterozygotes depends on the type of mutation coexisting with the p.H1069Q. One hundred forty-two patients with clinically, biochemically, and genetically diagnosed WD were studied. The mutational analysis of ATP7B was performed by direct sequencing. A total number of 26 mutations in ATP7B were identified. The p.His1069Gln was the most common mutation (allelic frequency: 72%). Seventy-three patients were homozygous for this mutation. Of compound heterozygotes, 37 had frameshift/nonsense mutation, and 20 had other missense mutation on one of their ATP7B alleles. Twelve patients had two non-p.H1069Q mutations. Patients homozygous for the p.H1069Q mutation had the less severe disturbances of copper metabolism and the latest presentation of first WD symptoms. The most severely disturbed copper metabolism and the earliest age at initial disease manifestation was noticed in non-p.H1069Q patients. In compound heterozygotes, the type of mutation coexisting with the p.H1069Q to a small extent influenced WD phenotype. The phenotype of WD varied considerably among patients with the same genotype. The p.H1069Q mutation is associated with late WD manifestation and with a mild disruption of copper metabolism. In compound heterozygotes, the phenotype of WD to a small extent depends on the type of mutation coexisting with the p.H1069Q. Besides genotype, additional modifying factors seem to determine WD manifestations. Copyright (c) 2005 Movement Disorder Society.

  18. 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

  19. Fate and Transport of Colloidal Energetic Residues

    DTIC Science & Technology

    2015-07-01

    Vadose Zone J 3(1): 262-270. 8. Davis, A. P., M. Shokouhian, and S. Ni. 2001. Loading estimates of lead , copper, cadmium , and zinc in urban...received the mm-sized Comp B. This particulate transport increases the effective contact time between residues and infiltrating rainwater, leading ...that natural mineral colloids can enhance transport of RDX and TNT by up to 15% and 20%, respectively. RDX and TNT attachment to natural colloids

  20. Effect of age and rainfall pH on contaminant yields from metal roofs.

    PubMed

    Wicke, Daniel; Cochrane, Thomas A; O'Sullivan, Aisling D; Cave, Simon; Derksen, Mark

    2014-01-01

    Metal roofs are recognized for conveying significant metal loads to urban streams through stormwater runoff. Metal concentrations in urban runoff depend on roof types and prevailing weather conditions but the combined effects of roof age and rainfall pH on metal mobilization are not well understood. To investigate these effects on roof runoff, water quality was analysed from galvanized iron and copper roofs following rainfall events and also from simulating runoff using a rainfall simulator on specially constructed roof modules. Zinc and copper yields under different pH regimes were investigated for two roof materials and two different ages. Metal mobilization from older roofs was greater than new roofs with 55-year-old galvanized roof surfaces yielding more Zn, on average increasing by 45% and 30% under a rainfall pH of 4 and 8, respectively. Predominantly dissolved (85-95%) Zn and Cu concentrations in runoff exponentially increased as the rainfall pH decreased. Results also confirmed that copper guttering and downpipes associated with galvanized steel roof systems can substantially increase copper levels in roof runoff. Understanding the dynamics of roof surfaces as a function of weathering and rainfall pH regimes can help developers with making better choices about roof types and materials for stormwater improvement.

  1. Analyte chemisorption and sensing on n- and p-channel copper phthalocyanine thin-film transistors.

    PubMed

    Yang, Richard D; Park, Jeongwon; Colesniuc, Corneliu N; Schuller, Ivan K; Royer, James E; Trogler, William C; Kummel, Andrew C

    2009-04-28

    Chemical sensing properties of phthalocyanine thin-film transistors have been investigated using nearly identical n- and p-channel devices. P-type copper phthalocyanine (CuPc) has been modified with fluorine groups to convert the charge carriers from holes to electrons. The sensor responses to the tight binding analyte dimethyl methylphosphonate (DMMP) and weak binding analyte methanol (MeOH) were compared in air and N(2). The results suggest that the sensor response involves counterdoping of pre-adsorbed oxygen (O(2)). A linear dependence of chemical response to DMMP concentration was observed in both n- and p- type devices. For DMMP, there is a factor of 2.5 difference in the chemical sensitivity between n- and p-channel CuPc thin-film transistors, even though it has similar binding strength to n- and p-type CuPc molecules as indicated by the desorption times. The effect is attributed to the difference in the analyte perturbation of electron and hole trap energies in n- and p-type materials.

  2. Copper chaperone Atox1 plays role in breast cancer cell migration.

    PubMed

    Blockhuys, Stéphanie; Wittung-Stafshede, Pernilla

    2017-01-29

    Copper (Cu) is an essential transition metal ion required as cofactor in many key enzymes. After cell uptake of Cu, the metal is transported by the cytoplasmic Cu chaperone Atox1 to P 1B -type ATPases in the Golgi network for incorporation into Cu-dependent enzymes in the secretory path. Cu is vital for many steps of cancer progression and Atox1 was recently suggested to have additional functionality as a nuclear transcription factor. We here investigated the expression level, cellular localization and role in cell migration of Atox1 in an aggressive breast cancer cell line upon combining immunostaining, microscopy and a wound healing assay. We made the unexpected discovery that Atox1 accumulates at lamellipodia borders of migrating cancer cells and Atox1 silencing resulted in migration defects as evidenced from reduced wound closure. Therefore, we have discovered an unknown role of the Cu chaperone Atox1 in breast cancer cell migration. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

  3. Solution-processed p-type copper(I) thiocyanate (CuSCN) for low-voltage flexible thin-film transistors and integrated inverter circuits

    NASA Astrophysics Data System (ADS)

    Petti, Luisa; Pattanasattayavong, Pichaya; Lin, Yen-Hung; Münzenrieder, Niko; Cantarella, Giuseppe; Yaacobi-Gross, Nir; Yan, Feng; Tröster, Gerhard; Anthopoulos, Thomas D.

    2017-03-01

    We report on low operating voltage thin-film transistors (TFTs) and integrated inverters based on copper(I) thiocyanate (CuSCN) layers processed from solution at low temperature on free-standing plastic foils. As-fabricated coplanar bottom-gate and staggered top-gate TFTs exhibit hole-transporting characteristics with average mobility values of 0.0016 cm2 V-1 s-1 and 0.013 cm2 V-1 s-1, respectively, current on/off ratio in the range 102-104, and maximum operating voltages between -3.5 and -10 V, depending on the gate dielectric employed. The promising TFT characteristics enable fabrication of unipolar NOT gates on flexible free-standing plastic substrates with voltage gain of 3.4 at voltages as low as -3.5 V. Importantly, discrete CuSCN transistors and integrated logic inverters remain fully functional even when mechanically bent to a tensile radius of 4 mm, demonstrating the potential of the technology for flexible electronics.

  4. 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.

  5. 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.

  6. Paths and determinants for Penicillium janthinellum to resist low and high copper

    PubMed Central

    Xu, Jian; Chen, Guo-Li; Sun, Xue-Zhe; Fan, Xian-Wei; You-Zhi, Li

    2015-01-01

    Copper (Cu) tolerance was well understood in fungi yeasts but not in filamentous fungi. Filamentous fungi are eukaryotes but unlike eukaryotic fungi yeasts, which are a collection of various fungi that are maybe classified into different taxa but all characterized by growth as filamentous hyphae cells and with a complex morphology. The current knowledge of Cu resistance of filamentous fungi is still fragmental and therefore needs to be bridged. In this study, we characterized Cu resistance of Penicillium janthinellum strain GXCR and its Cu-resistance-decreasing mutants (EC-6 and UC-8), and conducted sequencing of a total of 6 transcriptomes from wild-type GXCR and mutant EC-6 grown under control and external Cu. Taken all the results together, Cu effects on the basal metabolism were directed to solute transport by two superfamilies of solute carrier and major facilitator, the buffering free CoA and Acyl-CoA pool in the peroxisome, F-type H+-transporting ATPases-based ATP production, V-type H+-transporting ATPases-based transmembrane transport, protein degradation, and alternative splicing of pre-mRNAs. Roles of enzymatic and non-enzymatic antioxidants in resistance to low and high Cu were defined. The backbone paths, signaling systems, and determinants that involve resistance of filamentous fungi to high Cu were determined, discussed and outlined in a model. PMID:26265593

  7. An improved performance of copper phthalocyanine OFETs with channel and source/drain contact modifications

    NASA Astrophysics Data System (ADS)

    Huanqin, Dang; Xiaoming, Wu; Xiaowei, Sun; Runqiu, Zou; Ruochuan, Zhang; Shougen, Yin

    2015-10-01

    We report an effective method to improve the performance of p-type copper phthalocyanine (CuPc) based organic field-effect transistors (OFETs) by employing a thin para-quaterphenyl (p-4p) film and simultaneously applying V2O5 to the source/drain regions. The p-4p layer was inserted between the insulating layer and the active layer, and V2O5 layer was added between CuPc and Al in the source-drain (S/D) area. As a result, the field-effect saturation mobility and on/off current ratio of the optimized device were improved to 5 × 10-2 cm2/(V·s) and 104, respectively. We believe that because p-4p could induce CuPc to form a highly oriented and continuous film, this resulted in the better injection and transport of the carriers. Moreover, by introducing the V2O5 electrode's modified layers, the height of the carrier injection barrier could be effectively tuned and the contact resistance could be reduced. Project supported by the National Natural Science Foundation of China (No. 60676051), the National High Technology Research and Development Program of China (No. 2013A A014201), the Scientific Developing Foundation of Tianjin Education Commission (No. 2011ZD02), the Key Science and Technology Support Program of Tianjin (No. 14ZCZDGX00006), and the Foundation of Key Discipline of Material Physics and Chemistry of Tianjin.

  8. Assessment of metal transport into and out of Terrace Reservoir, Conejos County, Colorado, April 1994 through March 1995; interim report

    USGS Publications Warehouse

    Ferguson, Sheryl; Edelmann, Patrick

    1996-01-01

    Terrace Reservoir is the primary source of water for crops and livestock in the southwestern part of the San Luis Valley in southern Colorado. Mining activities have occurred in the basin for more than 100 years, and substantial mining of gold has occurred intermittently at the Summitville Mine.Historically, the Summitville Mine site has produced highly acidic, metal-enriched water that drained from the mine site into Wightman Fork and flowed to the Alamosa River and Terrace Reservoir. In 1994, a study was begun as part of risk-assessment and remediation efforts and to evaluate metal transport into and out of Terrace Reservoir. During the study period, the pH immediately upstream from Terrace Reservoir ranged from 4.3 to 7.8. The highest pH occurred during the pre-peak snowmelt period; the lowest pH occurred during storm runoff during summer. Downstream from Terrace Reservoir, the pH ranged from 4.6 to 7.6. The highest pH occurred during the pre-peak snowmelt period, and the lowest pH occurred during summer in mid-July. A comparison of the streamflow hydrographs upstream and downstream from Terrace Reservoir indicated that there was only a small difference between the annual volume of water that entered the reservoir and the annual volume of water that was released from the reservoir. Large spatial and temporal variations in concentrations of the metals of concern occurred during the study.The median and maximum concentrations of dissolved and total aluminum, iron, copper, cadmium, manganese, and zinc were larger upstream from the reservoir than downstream from the reservoir. The largest concentrations of dissolved aluminum, iron, copper, cadmium, manganese, and zinc generally occurred between mid-June and November. Throughout the study, aluminum was transported into the reservoir predominantly in the particulate or suspended form. Downstream from the reservoir, the suspended-aluminum fraction was predominant only during the pre-peak snowmelt and peak snowmelt periods. The temporal variations in the percentage of dissolved and suspended fraction of iron and copper downstream from Terrace Reservoir were similar to the temporal variations that occurred upstream from the reservoir. During the study period, cadmium, manganese, and zinc generally were transported into and out of the reservoir predominantly in the dissolved form. Metal loads varied considerably as a result of changes in streamflow or changes in metal concentrations, or both. The largest daily loads of aluminum, iron, and manganese were transported into and out of Terrace Reservoir during the peak snowmelt period.The reservoir was a sink for an estimated 294 tons of aluminum and 596 tons of iron. However, about 68.5 tons of total aluminum and about 194 tons of total iron were transported out of the reservoir during the study period. During the study period, about 22\\x11tons of total copper remained in the reservoir, and 39 tons was transported downstream from the reservoir. About 47 tons of total manganese and 18 tons of total-zinc loads were transported out of the reservoir; the reservoir was a sink for only a small fraction of total-manganese and -zinc.

  9. A promising p-type transparent conducting material: Layered oxysulfide [Cu2S2][Sr3Sc2O5

    NASA Astrophysics Data System (ADS)

    Liu, Min-Ling; Wu, Li-Bin; Huang, Fu-Qiang; Chen, Li-Dong; Chen, I.-Wei

    2007-12-01

    Sr3Cu2Sc2O5S2, a layered oxysulfide, composed of anti-PbO-like [Cu2S2] slabs alternating with perovskitelike [Sr3Sc2O5] slabs, was systematically studied as a p-type transparent conducting material. The material has a wide energy gap of 3.1eV and a p-type electrical conductivity of 2.8Scm-1 at room temperature. The hole mobility of +150cm2V-1S-1 at room temperature, which is much higher than the typical value of ˜10-1-10width="0.3em"/>cm2V-1S-1 found in other copper compounds. The performances of bulk undoped Sr3Cu2Sc2O5S2 show the promise of copper oxysulfides as a class of p-type transparent conductive materials that is essential for optoelectronic applications.

  10. Electronic structure, transport, and collective effects in molecular layered systems.

    PubMed

    Hahn, Torsten; Ludwig, Tim; Timm, Carsten; Kortus, Jens

    2017-01-01

    The great potential of organic heterostructures for organic device applications is exemplified by the targeted engineering of the electronic properties of phthalocyanine-based systems. The transport properties of two different phthalocyanine systems, a pure copper phthalocyanine (CoPc) and a flourinated copper phthalocyanine-manganese phthalocyanine (F 16 CoPc/MnPc) heterostructure, are investigated by means of density functional theory (DFT) and the non-equilibrium Green's function (NEGF) approach. Furthermore, a master-equation-based approach is used to include electronic correlations beyond the mean-field-type approximation of DFT. We describe the essential theoretical tools to obtain the parameters needed for the master equation from DFT results. Finally, an interacting molecular monolayer is considered within a master-equation approach.

  11. Structural and electronic properties of copper-doped chalcogenide glasses

    NASA Astrophysics Data System (ADS)

    Guzman, David M.; Strachan, Alejandro

    2017-10-01

    Using ab initio molecular dynamics based on density functional theory, we study the atomic and electronic structure, and transport properties of copper-doped germanium-based chalcogenide glasses. These mixed ionic-electronic conductor materials exhibit resistance or threshold switching under external electric field depending on slight variations of chemical composition. Understanding the origin of the transport character is essential for the functionalization of glassy chalcogenides for nanoelectronics applications. To this end, we generated atomic structures for GeX3 and GeX6 (X = S, Se, Te) at different copper concentrations and characterized the atomic origin of electronic states responsible for transport and the tendency of copper clustering as a function of metal concentration. Our results show that copper dissolution energies explain the tendency of copper to agglomerate in telluride glasses, consistent with filamentary conduction. In contrast, copper is less prone to cluster in sulfides and selenides leading to hysteresisless threshold switching where the nature of transport is dominated by electronic midgap defects derived from polar chalcogen bonds and copper atoms. Simulated I -V curves show that at least 35% by weight of copper is required to achieve the current demands of threshold-based devices for memory applications.

  12. Copper Deficiency Leads to Anemia, Duodenal Hypoxia, Upregulation of HIF-2α and Altered Expression of Iron Absorption Genes in Mice

    PubMed Central

    Matak, Pavle; Zumerle, Sara; Mastrogiannaki, Maria; El Balkhi, Souleiman; Delga, Stephanie; Mathieu, Jacques R. R.; Canonne-Hergaux, François; Poupon, Joel; Sharp, Paul A.; Vaulont, Sophie; Peyssonnaux, Carole

    2013-01-01

    Iron and copper are essential trace metals, actively absorbed from the proximal gut in a regulated fashion. Depletion of either metal can lead to anemia. In the gut, copper deficiency can affect iron absorption through modulating the activity of hephaestin - a multi-copper oxidase required for optimal iron export from enterocytes. How systemic copper status regulates iron absorption is unknown. Mice were subjected to a nutritional copper deficiency-induced anemia regime from birth and injected with copper sulphate intraperitoneally to correct the anemia. Copper deficiency resulted in anemia, increased duodenal hypoxia and Hypoxia inducible factor 2α (HIF-2α) levels, a regulator of iron absorption. HIF-2α upregulation in copper deficiency appeared to be independent of duodenal iron or copper levels and correlated with the expression of iron transporters (Ferroportin - Fpn, Divalent Metal transporter – Dmt1) and ferric reductase – Dcytb. Alleviation of copper-dependent anemia with intraperitoneal copper injection resulted in down regulation of HIF-2α-regulated iron absorption genes in the gut. Our work identifies HIF-2α as an important regulator of iron transport machinery in copper deficiency. PMID:23555700

  13. Hole transport in pure and doped hematite

    NASA Astrophysics Data System (ADS)

    Liao, Peilin; Carter, Emily A.

    2012-07-01

    Hematite (α-Fe2O3) is a promising candidate for use in photovoltaic (PV) and photoelectrochemical devices. Its poor conductivity is one major drawback. Doping hematite either p-type or n-type greatly enhances its measured conductivity and is required for potential p-n junctions in PVs. Here, we study hole transport in pure and doped hematite using an electrostatically embedded cluster model with ab initio quantum mechanics (unrestricted Hartree-Fock theory). Consistent with previous work, the model suggests that hole hopping is via oxygen anions for pure hematite. The activation energy for hole mobility is predicted to be at least 0.1 eV higher than the activation energy for electron mobility, consistent with the trend observed in experiments. We examine four dopants—magnesium(II), nickel(II), copper(II), and manganese(II/III) in direct cation substitution sites—to gain insight into the mechanism by which conductivity is improved. The activation energies are used to assess qualitative effects of different dopants. The hole carriers are predicted to be attracted to O anions near the dopants. The magnitude of the trapping effect is similar among the four dopants in their +2 oxidation states. The multivalent character of Mn doping facilitates local hole transport around Mn centers via a low-barrier O-Mn-O pathway, which suggests that higher hole mobility can be achieved with increasing Mn doping concentration, especially when a network of these low-barrier pathways is produced. Our results suggest that the experimentally observed conductivity increase in Mg-, Ni-, and Cu-doped p-type hematite is mostly due to an increase in hole carriers rather than improved mobility, and that Mg-, Ni-, and Cu-doping perform similarly, while the conductivity of Mn-doped hematite might be significantly improved in the high doping concentration limit.

  14. 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.

  15. 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.

  16. 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.

  17. Copper transport into the secretory pathway is regulated by oxygen in macrophages

    PubMed Central

    White, Carine; Kambe, Taiho; Fulcher, Yan G.; Sachdev, Sherri W.; Bush, Ashley I.; Fritsche, Kevin; Lee, Jaekwon; Quinn, Thomas P.; Petris, Michael J.

    2009-01-01

    Summary Copper is an essential nutrient for a variety of biochemical processes; however, the redox properties of copper also make it potentially toxic in the free form. Consequently, the uptake and intracellular distribution of this metal is strictly regulated. This raises the issue of whether specific pathophysiological conditions can promote adaptive changes in intracellular copper distribution. In this study, we demonstrate that oxygen limitation promotes a series of striking alterations in copper homeostasis in RAW264.7 macrophage cells. Hypoxia was found to stimulate copper uptake and to increase the expression of the copper importer, CTR1. This resulted in increased copper delivery to the ATP7A copper transporter and copper-dependent trafficking of ATP7A to cytoplasmic vesicles. Significantly, the ATP7A protein was required to deliver copper into the secretory pathway to ceruloplasmin, a secreted copperdependent enzyme, the expression and activity of which were stimulated by hypoxia. However, the activities of the alternative targets of intracellular copper delivery, superoxide dismutase and cytochrome c oxidase, were markedly reduced in response to hypoxia. Collectively, these findings demonstrate that copper delivery into the biosynthetic secretory pathway is regulated by oxygen availability in macrophages by a selective increase in copper transport involving ATP7A. PMID:19351718

  18. Preparation and characterization of copper telluride thin films by modified chemical bath deposition (M-CBD) method

    NASA Astrophysics Data System (ADS)

    Pathan, H. M.; Lokhande, C. D.; Amalnerkar, D. P.; Seth, T.

    2003-09-01

    Copper telluride thin films were deposited using modified chemical method using copper(II) sulphate; pentahydrate [CuSO 4·5H 2O] and sodium tellurite [Na 2TeO 3] as cationic and anionic sources, respectively. Modified chemical method is based on the immersion of the substrate into separately placed cationic and anionic precursors. The preparative conditions such as concentration, pH, immersion time, immersion cycles, etc. were optimized to get good quality copper telluride thin films at room temperature. The films have been characterized for structural, compositional, optical and electrical transport properties by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Rutherford back scattering (RBS), optical absorption/transmission, electrical resistivity and thermoemf measurement techniques.

  19. Eco-friendly p-type Cu2SnS3 thermoelectric material: crystal structure and transport properties

    PubMed Central

    Shen, Yawei; Li, Chao; Huang, Rong; Tian, Ruoming; Ye, Yang; Pan, Lin; Koumoto, Kunihito; Zhang, Ruizhi; Wan, Chunlei; Wang, Yifeng

    2016-01-01

    As a new eco-friendly thermoelectric material, copper tin sulfide (Cu2SnS3) ceramics were experimentally studied by Zn-doping. Excellent electrical transport properties were obtained by virtue of 3-dimensionally conductive network for holes, which are less affected by the coexistence of cubic and tetragonal phases that formed upon Zn subsitition for Sn; a highest power factors ~0.84 mW m−1 K−2 at 723 K was achieved in the 20% doped sample. Moreover, an ultralow lattice thermal conductivity close to theoretical minimum was observed in these samples, which could be related to the disordering of atoms in the coexisting cubic and tetragonal phases and the interfaces. Thanks to the phonon-glass-electron-crystal features, a maximum ZT ~ 0.58 was obtained at 723 K, which stands among the tops for sulfide thermoelectrics at the same temperature. PMID:27666524

  20. 49 CFR 192.125 - Design of copper pipe.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 3 2013-10-01 2013-10-01 false Design of copper pipe. 192.125 Section 192.125 Transportation Other Regulations Relating to Transportation (Continued) PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) PIPELINE SAFETY TRANSPORTATION OF NATURAL AND OTHER GAS BY PIPELINE: MINIMUM FEDERA...

  1. Identification of Two Conserved Residues Involved in Copper Release from Chloroplast PIB-1-ATPases*

    PubMed Central

    Sautron, Emeline; Giustini, Cécile; Dang, ThuyVan; Moyet, Lucas; Salvi, Daniel; Crouzy, Serge; Rolland, Norbert; Catty, Patrice; Seigneurin-Berny, Daphné

    2016-01-01

    Copper is an essential transition metal for living organisms. In the plant model Arabidopsis thaliana, half of the copper content is localized in the chloroplast, and as a cofactor of plastocyanin, copper is essential for photosynthesis. Within the chloroplast, copper delivery to plastocyanin involves two transporters of the PIB-1-ATPases subfamily: HMA6 at the chloroplast envelope and HMA8 in the thylakoid membranes. Both proteins are high affinity copper transporters but share distinct enzymatic properties. In the present work, the comparison of 140 sequences of PIB-1-ATPases revealed a conserved region unusually rich in histidine and cysteine residues in the TMA-L1 region of eukaryotic chloroplast copper ATPases. To evaluate the role of these residues, we mutated them in HMA6 and HMA8. Mutants of interest were selected from phenotypic tests in yeast and produced in Lactococcus lactis for further biochemical characterizations using phosphorylation assays from ATP and Pi. Combining functional and structural data, we highlight the importance of the cysteine and the first histidine of the CX3HX2H motif in the process of copper release from HMA6 and HMA8 and propose a copper pathway through the membrane domain of these transporters. Finally, our work suggests a more general role of the histidine residue in the transport of copper by PIB-1-ATPases. PMID:27493208

  2. Repercussion of Solid state vs. Liquid state synthesized p-n heterojunction RGO-copper phosphate on proton reduction potential in water.

    PubMed

    Samal, Alaka; Das, Dipti P; Madras, Giridhar

    2018-02-13

    The same copper phosphate catalysts were synthesized by obtaining the methods involving solid state as well as liquid state reactions in this work. And then the optimised p-n hybrid junction photocatalysts have been synthesized following the same solid/liquid reaction pathways. The synthesized copper phosphate photocatalyst has unique rod, flower, caramel-treat-like morphology. The Mott-Schottky behavior is in accordance with the expected behavior of n-type semiconductor and the carrier concentration was calculated using the M-S analysis for the photocatalyst. And for the p-n hybrid junction of 8RGO-Cu 3 (PO 4 ) 2 -PA (PA abbreviated for photoassisted synthesis method), 8RGO-Cu 3 (PO 4 ) 2 -EG(EG abbreviated for Ethylene Glycol based synthesis method), 8RGO-Cu 3 (PO 4 ) 2 -PEG (PEG abbreviated for Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol based synthesis method)the amount of H 2 synthesized was 7500, 6500 and 4500 µmol/h/g, respectively. The excited electrons resulting after the irradiation of visible light on the CB of p-type reduced graphene oxide (RGO) migrate easily to n-type Cu 3 (PO 4 ) 2 via. the p-n junction interfaces and hence great charge carrier separation was achieved.

  3. 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.

  4. Thermoelectric transport in Cu7PSe6 with high copper ionic mobility.

    PubMed

    Weldert, Kai S; Zeier, Wolfgang G; Day, Tristan W; Panthöfer, Martin; Snyder, G Jeffrey; Tremel, Wolfgang

    2014-08-27

    Building on the good thermoelectric performances of binary superionic compounds like Cu2Se, Ag2Se and Cu2S, a better and more detailed understanding of phonon-liquid electron-crystal (PLEC) thermoelectric materials is desirable. In this work we present the thermoelectric transport properties of the compound Cu7PSe6 as the first representative of the class of argyrodite-type ion conducting thermoelectrics. With a huge variety of possible compositions and high ionic conductivity even at room temperature, the argyrodites represent a very good model system to study structure-property relationships for PLEC thermoelectric materials. We particularly highlight the extraordinary low thermal conductivity of Cu7PSe6 below the glass limit, which can be associated with the molten copper sublattice leading to a softening of phonon modes.

  5. An in-situ phosphorus source for the synthesis of Cu 3P and the subsequent conversion to Cu 3PS 4 nanoparticle clusters

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

    Sheets, Erik J.; Stach, Eric A.; Yang, Wei -Chang

    2015-09-20

    The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I-V-VI chalcogenides including copper phosphide (Cu 3P) and copper thiophosphate (Cu 3PS 4). Herein, we report a one-pot, solution-based synthesis of Cu 3P nanocrystals utilizing an in-situ phosphorus source: phosphorus pentasulfide (P 2S 5) in trioctylphosphine (TOP). By injecting this phosphorus source into a copper solution in oleylamine (OLA), uniform and size controlled Cu 3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cumore » 3P nanocrystals with decomposing thiourea forms nanoscale Cu 3PS 4 particles having p-type conductivity and an effective optical band gap of 2.36 eV.« less

  6. Impairment of Interrelated Iron- and Copper Homeostatic Mechanisms in Brain Contributes to the Pathogenesis of Neurodegenerative Disorders

    PubMed Central

    Skjørringe, Tina; Møller, Lisbeth Birk; Moos, Torben

    2012-01-01

    Iron and copper are important co-factors for a number of enzymes in the brain, including enzymes involved in neurotransmitter synthesis and myelin formation. Both shortage and an excess of iron or copper will affect the brain. The transport of iron and copper into the brain from the circulation is strictly regulated, and concordantly protective barriers, i.e., the blood-brain barrier (BBB) and the blood-cerebrospinal fluid (CSF) barrier (BCB) have evolved to separate the brain environment from the circulation. The uptake mechanisms of the two metals interact. Both iron deficiency and overload lead to altered copper homeostasis in the brain. Similarly, changes in dietary copper affect the brain iron homeostasis. Moreover, the uptake routes of iron and copper overlap each other which affect the interplay between the concentrations of the two metals in the brain. The divalent metal transporter-1 (DMT1) is involved in the uptake of both iron and copper. Furthermore, copper is an essential co-factor in numerous proteins that are vital for iron homeostasis and affects the binding of iron-response proteins to iron-response elements in the mRNA of the transferrin receptor, DMT1, and ferroportin, all highly involved in iron transport. Iron and copper are mainly taken up at the BBB, but the BCB also plays a vital role in the homeostasis of the two metals, in terms of sequestering, uptake, and efflux of iron and copper from the brain. Inside the brain, iron and copper are taken up by neurons and glia cells that express various transporters. PMID:23055972

  7. 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.

  8. The copper metallome in eukaryotic cells.

    PubMed

    Vest, Katherine E; Hashemi, Hayaa F; Cobine, Paul A

    2013-01-01

    Copper is an element that is both essential and toxic. It is a required micronutrient for energy production in aerobic eukaryotes, from unicellular yeast to plants and mammals. Copper is also required for the acquisition and systemic distribution of the essential metal iron, and so copper deficiency results in iron deficiency. Copper enzymes have been identified that explain the wide variety of symptoms suffered by copper deficient subjects. The cloning of the genes encoding transport proteins responsible for copper-related Menkes and Wilson diseases inspired and coincided with the discovery of copper chaperones that stimulated the copper homeostasis field. Copper continues to be implicated in new array of proteins, notably those involved in a variety of neurodegenerative diseases. Here we will describe the cadre of important historical copper proteins and survey the major metallochaperones and transporters responsible for mobilization and sequestration of copper in yeast, mammals and plants.

  9. 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.

  10. Synthesis, characterization and biological activities of semicarbazones and their copper complexes.

    PubMed

    Venkatachalam, Taracad K; Bernhardt, Paul V; Noble, Chris J; Fletcher, Nicholas; Pierens, Gregory K; Thurecht, Kris J; Reutens, David C

    2016-09-01

    Substituted semicarbazones/thiosemicarbazones and their copper complexes have been prepared and several single crystal structures examined. The copper complexes of these semicarbazone/thiosemicarbazones were prepared and several crystal structures examined. The single crystal X-ray structure of the pyridyl-substituted semicarbazone showed two types of copper complexes, a monomer and a dimer. We also found that the p-nitrophenyl semicarbazone formed a conventional 'magic lantern' acetate-bridged dimer. Electron Paramagnetic Resonance (EPR) of several of the copper complexes was consistent with the results of single crystal X-ray crystallography. The EPR spectra of the p-nitrophenyl semicarbazone copper complex in dimethylsulfoxide (DMSO) showed the presence of two species, confirming the structural information. Since thiosemicarbazones and semicarbazones have been reported to exhibit anticancer activity, we examined the anticancer activity of several of the derivatives reported in the present study and interestingly only the thiosemicarbazone showed activity while the semicarbazones were not active indicating that introduction of sulphur atom alters the biological profile of these thiosemicarbazones. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Identification of two novel mutations in the SLC45A2 gene in a Hungarian pedigree affected by unusual OCA type 4.

    PubMed

    Tóth, Lola; Fábos, Beáta; Farkas, Katalin; Sulák, Adrienn; Tripolszki, Kornélia; Széll, Márta; Nagy, Nikoletta

    2017-03-15

    Oculocutaneous albinism (OCA) is a clinically and genetically heterogenic group of pigmentation abnormalities. OCA type IV (OCA4, OMIM 606574) develops due to homozygous or compound heterozygous mutations in the solute carrier family 45, member 2 (SLC45A2) gene. This gene encodes a membrane-associated transport protein, which regulates tyrosinase activity and, thus, melanin content by changing melanosomal pH and disrupting the incorporation of copper into tyrosinase. Here we report two Hungarian siblings affected by an unusual OCA4 phenotype. After genomic DNA was isolated from peripheral blood of the patients, the coding regions of the SLC45A2 gene were sequenced. In silico tools were applied to identify the functional impact of the newly detected mutations. Direct sequencing of the SLC45A2 gene revealed two novel, heterozygous mutations, one missense (c.1226G > A, p.Gly409Asp) and one nonsense (c.1459C > T, p.Gln437*), which were present in both patients, suggesting the mutations were compound heterozygous. In silico tools suggest that these variations are disease causing mutations. The newly identified mutations may affect the transmembrane domains of the protein, and could impair transport function, resulting in decreases in both melanosomal pH and tyrosinase activity. Our study provides expands on the mutation spectrum of the SLC45A2 gene and the genetic background of OCA4.

  12. Transparent flexible thermoelectric material based on non-toxic earth-abundant p-type copper iodide thin film

    PubMed Central

    Yang, C.; Souchay, D.; Kneiß, M.; Bogner, M.; Wei, H. M.; Lorenz, M.; Oeckler, O.; Benstetter, G.; Fu, Y. Q.; Grundmann, M.

    2017-01-01

    Thermoelectric devices that are flexible and optically transparent hold unique promise for future electronics. However, development of invisible thermoelectric elements is hindered by the lack of p-type transparent thermoelectric materials. Here we present the superior room-temperature thermoelectric performance of p-type transparent copper iodide (CuI) thin films. Large Seebeck coefficients and power factors of the obtained CuI thin films are analysed based on a single-band model. The low-thermal conductivity of the CuI films is attributed to a combined effect of the heavy element iodine and strong phonon scattering. Accordingly, we achieve a large thermoelectric figure of merit of ZT=0.21 at 300 K for the CuI films, which is three orders of magnitude higher compared with state-of-the-art p-type transparent materials. A transparent and flexible CuI-based thermoelectric element is demonstrated. Our findings open a path for multifunctional technologies combing transparent electronics, flexible electronics and thermoelectricity. PMID:28681842

  13. Transparent flexible thermoelectric material based on non-toxic earth-abundant p-type copper iodide thin film.

    PubMed

    Yang, C; Souchay, D; Kneiß, M; Bogner, M; Wei, H M; Lorenz, M; Oeckler, O; Benstetter, G; Fu, Y Q; Grundmann, M

    2017-07-06

    Thermoelectric devices that are flexible and optically transparent hold unique promise for future electronics. However, development of invisible thermoelectric elements is hindered by the lack of p-type transparent thermoelectric materials. Here we present the superior room-temperature thermoelectric performance of p-type transparent copper iodide (CuI) thin films. Large Seebeck coefficients and power factors of the obtained CuI thin films are analysed based on a single-band model. The low-thermal conductivity of the CuI films is attributed to a combined effect of the heavy element iodine and strong phonon scattering. Accordingly, we achieve a large thermoelectric figure of merit of ZT=0.21 at 300 K for the CuI films, which is three orders of magnitude higher compared with state-of-the-art p-type transparent materials. A transparent and flexible CuI-based thermoelectric element is demonstrated. Our findings open a path for multifunctional technologies combing transparent electronics, flexible electronics and thermoelectricity.

  14. 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.

  15. Copper import in Escherichia coli by the yersiniabactin metallophore system

    PubMed Central

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

    2017-01-01

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

  16. The response of Isidorella newcombi to copper exposure: Using an integrated biological framework to interpret transcriptomic responses from RNA-seq analysis.

    PubMed

    Ubrihien, Rodney P; Ezaz, Tariq; Taylor, Anne M; Stevens, Mark M; Krikowa, Frank; Foster, Simon; Maher, William A

    2017-04-01

    This study describes the transcriptomic response of the Australian endemic freshwater gastropod Isidorella newcombi exposed to 80±1μg/L of copper for 3days. Analysis of copper tissue concentration, lysosomal membrane destabilisation and RNA-seq were conducted. Copper tissue concentrations confirmed that copper was bioaccumulated by the snails. Increased lysosomal membrane destabilisation in the copper-exposed snails indicated that the snails were stressed as a result of the exposure. Both copper tissue concentrations and lysosomal destabilisation were significantly greater in snails exposed to copper. In order to interpret the RNA-seq data from an ecotoxicological perspective an integrated biological response model was developed that grouped transcriptomic responses into those associated with copper transport and storage, survival mechanisms and cell death. A conceptual model of expected transcriptomic changes resulting from the copper exposure was developed as a basis to assess transcriptomic responses. Transcriptomic changes were evident at all the three levels of the integrated biological response model. Despite lacking statistical significance, increased expression of the gene encoding copper transporting ATPase provided an indication of increased internal transport of copper. Increased expression of genes associated with endocytosis are associated with increased transport of copper to the lysosome for storage in a detoxified form. Survival mechanisms included metabolic depression and processes associated with cellular repair and recycling. There was transcriptomic evidence of increased cell death by apoptosis in the copper-exposed organisms. Increased apoptosis is supported by the increase in lysosomal membrane destabilisation in the copper-exposed snails. Transcriptomic changes relating to apoptosis, phagocytosis, protein degradation and the lysosome were evident and these processes can be linked to the degradation of post-apoptotic debris. The study identified contaminant specific transcriptomic markers as well as markers of general stress. From an ecotoxicological perspective, the use of a framework to group transcriptomic responses into those associated with copper transport, survival and cell death assisted with the complex process of interpretation of RNA-seq data. The broad adoption of such a framework in ecotoxicology studies would assist in comparison between studies and the identification of reliable transcriptomic markers of contaminant exposure and response. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. 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

  18. Genes for all metals--a bacterial view of the periodic table. The 1996 Thom Award Lecture.

    PubMed

    Silver, S

    1998-01-01

    Bacterial chromosomes have genes for transport proteins for inorganic nutrient cations and oxyanions, such as NH4+, K+, Mg2+, Co2+, Fe3+, Mn2+, Zn2+ and other trace cations, and PO4(3-), SO4(2-) and less abundant oxyanions. Together these account for perhaps a few hundred genes in many bacteria. Bacterial plasmids encode resistance systems for toxic metal and metalloid ions including Ag+, AsO2-, AsO4(3-), Cd2+, Co2+, CrO4(2-), Cu2+, Hg2+, Ni2+, Pb2+, TeO3(2-), Tl+ and Zn2+. Most resistance systems function by energy-dependent efflux of toxic ions. A few involve enzymatic (mostly redox) transformations. Some of the efflux resistance systems are ATPases and others are chemiosmotic ion/proton exchangers. The Cd(2+)-resistance cation pump of Gram-positive bacteria is membrane P-type ATPase, which has been labeled with 32P from [gamma-32P]ATP and drives ATP-dependent Cd2+ (and Zn2+) transport by membrane vesicles. The genes defective in the human hereditary diseases of copper metabolism, Menkes syndrome and Wilson's disease, encode P-type ATPases that are similar to bacterial cadmium ATPases. The arsenic resistance system transports arsenite [As(III)], alternatively with the ArsB polypeptide functioning as a chemiosmotic efflux transporter or with two polypeptides, ArsB and ArsA, functioning as an ATPase. The third protein of the arsenic resistance system is an enzyme that reduces intracellular arsenate [As(V)] to arsenite [As(III)], the substrate of the efflux system. In Gram-negative cells, a three polypeptide complex functions as a chemiosmotic cation/protein exchanger to efflux Cd2+, Zn2+ and Co2+. This pump consists of an inner membrane (CzcA), an outer membrane (CzcC) and a membrane-spanning (CzcB) protein that function together.

  19. Streptococcus mutans copper chaperone, CopZ, is critical for biofilm formation and competitiveness.

    PubMed

    Garcia, S S; Du, Q; Wu, H

    2016-12-01

    The oral cavity is a dynamic environment characterized by hundreds of bacterial species, saliva, and an influx of nutrients and metal ions such as copper. Although there is a physiologic level of copper in the saliva, the oral cavity is often challenged with an influx of copper ions. At high concentrations copper is toxic and must therefore be strictly regulated by pathogens for them to persist and cause disease. The cariogenic pathogen Streptococcus mutans manages excess copper using the copYAZ operon that encodes a negative DNA-binding repressor (CopY), the P1-ATPase copper exporter (CopA), and the copper chaperone (CopZ). These hypothetical roles of the copYAZ operon in regulation and copper transport to receptors led us to investigate their contribution to S. mutans virulence. Mutants defective in the copper chaperone CopZ, but not CopY or CopA, were impaired in biofilm formation and competitiveness against commensal streptococci. Characterization of the CopZ mutant biofilm revealed a decreased secretion of glucosyltransferases and reduced expression of mutacin genes. These data suggest that the function of copZ on biofilm and competitiveness is independent of copper resistance and CopZ is a global regulator for biofilm and other virulence factors. Further characterization of CopZ may lead to the identification of new biofilm pathways. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  20. Antimicrobial properties of ternary eutectic aluminum alloys.

    PubMed

    Hahn, Claudia; Hans, Michael; Hein, Christina; Dennstedt, Anne; Mücklich, Frank; Rettberg, Petra; Hellweg, Christine Elisabeth; Leichert, Lars Ingo; Rensing, Christopher; Moeller, Ralf

    2018-06-27

    Several Escherichia coli deletion mutants of the Keio collection were selected for analysis to better understand which genes may play a key role in copper or silver homeostasis. Each of the selected E. coli mutants had a deletion of a single gene predicted to encode proteins for homologous recombination or contained functions directly linked to copper or silver transport or transformation. The survival of these strains on pure copper surfaces, stainless steel, and alloys of aluminum, copper and/or silver was investigated. When exposed to pure copper surfaces, E. coli ΔcueO was the most sensitive, whereas E. coli ΔcopA was the most resistant amongst the different strains tested. However, we observed a different trend in sensitivities in E. coli strains upon exposure to alloys of the system Al-Ag-Cu. While minor antimicrobial effects were detected after exposure of E. coli ΔcopA and E. coli ΔrecA to Al-Ag alloys, no effect was detected after exposure to Al-Cu alloys. The release of copper ions and cell-associated copper ion concentrations were determined for E. coli ΔcopA and the wild-type E. coli after exposure to pure copper surfaces. Altogether, compared to binary alloys, ternary eutectic alloys (Al-Ag-Cu) had the highest antimicrobial effect and thus, warrant further investigation.

  1. COMMD1 is linked to the WASH complex and regulates endosomal trafficking of the copper transporter ATP7A

    PubMed Central

    Phillips-Krawczak, Christine A.; Singla, Amika; Starokadomskyy, Petro; Deng, Zhihui; Osborne, Douglas G.; Li, Haiying; Dick, Christopher J.; Gomez, Timothy S.; Koenecke, Megan; Zhang, Jin-San; Dai, Haiming; Sifuentes-Dominguez, Luis F.; Geng, Linda N.; Kaufmann, Scott H.; Hein, Marco Y.; Wallis, Mathew; McGaughran, Julie; Gecz, Jozef; van de Sluis, Bart; Billadeau, Daniel D.; Burstein, Ezra

    2015-01-01

    COMMD1 deficiency results in defective copper homeostasis, but the mechanism for this has remained elusive. Here we report that COMMD1 is directly linked to early endosomes through its interaction with a protein complex containing CCDC22, CCDC93, and C16orf62. This COMMD/CCDC22/CCDC93 (CCC) complex interacts with the multisubunit WASH complex, an evolutionarily conserved system, which is required for endosomal deposition of F-actin and cargo trafficking in conjunction with the retromer. Interactions between the WASH complex subunit FAM21, and the carboxyl-terminal ends of CCDC22 and CCDC93 are responsible for CCC complex recruitment to endosomes. We show that depletion of CCC complex components leads to lack of copper-dependent movement of the copper transporter ATP7A from endosomes, resulting in intracellular copper accumulation and modest alterations in copper homeostasis in humans with CCDC22 mutations. This work provides a mechanistic explanation for the role of COMMD1 in copper homeostasis and uncovers additional genes involved in the regulation of copper transporter recycling. PMID:25355947

  2. Copper Import into the Mitochondrial Matrix in Saccharomyces cerevisiae Is Mediated by Pic2, a Mitochondrial Carrier Family Protein*

    PubMed Central

    Vest, Katherine E.; Leary, Scot C.; Winge, Dennis R.; Cobine, Paul A.

    2013-01-01

    Saccharomyces cerevisiae must import copper into the mitochondrial matrix for eventual assembly of cytochrome c oxidase. This copper is bound to an anionic fluorescent molecule known as the copper ligand (CuL). Here, we identify for the first time a mitochondrial carrier family protein capable of importing copper into the matrix. In vitro transport of the CuL into the mitochondrial matrix was saturable and temperature-dependent. Strains with a deletion of PIC2 grew poorly on copper-deficient non-fermentable medium supplemented with silver and under respiratory conditions when challenged with a matrix-targeted copper competitor. Mitochondria from pic2Δ cells had lower total mitochondrial copper and exhibited a decreased capacity for copper uptake. Heterologous expression of Pic2 in Lactococcus lactis significantly enhanced CuL transport into these cells. Therefore, we propose a novel role for Pic2 in copper import into mitochondria. PMID:23846699

  3. Copper import into the mitochondrial matrix in Saccharomyces cerevisiae is mediated by Pic2, a mitochondrial carrier family protein.

    PubMed

    Vest, Katherine E; Leary, Scot C; Winge, Dennis R; Cobine, Paul A

    2013-08-16

    Saccharomyces cerevisiae must import copper into the mitochondrial matrix for eventual assembly of cytochrome c oxidase. This copper is bound to an anionic fluorescent molecule known as the copper ligand (CuL). Here, we identify for the first time a mitochondrial carrier family protein capable of importing copper into the matrix. In vitro transport of the CuL into the mitochondrial matrix was saturable and temperature-dependent. Strains with a deletion of PIC2 grew poorly on copper-deficient non-fermentable medium supplemented with silver and under respiratory conditions when challenged with a matrix-targeted copper competitor. Mitochondria from pic2Δ cells had lower total mitochondrial copper and exhibited a decreased capacity for copper uptake. Heterologous expression of Pic2 in Lactococcus lactis significantly enhanced CuL transport into these cells. Therefore, we propose a novel role for Pic2 in copper import into mitochondria.

  4. Evolution of electronic states in n-type copper oxide superconductor via electric double layer gating

    NASA Astrophysics Data System (ADS)

    Jin, Kui; Hu, Wei; Zhu, Beiyi; Kim, Dohun; Yuan, Jie; Sun, Yujie; Xiang, Tao; Fuhrer, Michael S.; Takeuchi, Ichiro; Greene, Richard. L.

    2016-05-01

    The occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2-xCexCuO4 (x = 0.15) ultrathin films, via the electric double layer transistor technique. Abnormal transport properties, such as multiple sign reversals of Hall resistivity in normal and mixed states, have been revealed within an electrostatic field in range of -2 V to + 2 V, as well as varying the temperature and magnetic field. In the mixed state, the intrinsic anomalous Hall conductivity invokes the contribution of both electron and hole-bands as well as the energy dependent density of states near the Fermi level. The two-band model can also describe the normal state transport properties well, whereas the carrier concentrations of electrons and holes are always enhanced or depressed simultaneously in electric fields. This is in contrast to the scenario of Fermi surface reconstruction by antiferromagnetism, where an anti-correlation is commonly expected.

  5. Metallicity of Ca 2Cu 6P 5 with single and double copper-pnictide layers

    DOE PAGES

    Li, Li; Parker, David; Chi, Miaofang; ...

    2016-02-16

    We report thermodynamic and transport properties, and also theoretical calculations, for Cu-based compound Ca 2Cu 6P 5 and compare with CaCu 2-δP 2. Both materials have layers of edge-sharing copper pnictide tetrahedral CuP 4, similar to Fe–As and Fe–Se layers (with FeAs 4, FeSe 4) in the iron-based superconductors. Despite the presence of this similar transition-metal pnictide layer, we find that both Ca 2Cu 6P 5 and CaCu 2-δP 2 have temperature-independent magnetic susceptibility and show metallic behavior with no evidence of either magnetic ordering or superconductivity down to 1.8 K CaCu 2-δP 2 is slightly off-stoichiometric, with δ =more » 0.14. Theoretical calculations suggest that unlike Fe 3d-based magnetic materials with a large density of states (DOS) at the Fermi surface, Cu have comparatively low DOS, with the majority of the 3d spectral weight located well below Fermi level. The room-temperature resistivity value of Ca 2Cu 6P 5 is only 9 μΩ-cm, due to a substantial plasma frequency and an inferred electron-phonon coupling λ of 0.073 (significantly smaller than that of metallic Cu). Also, microscopy result shows that Cu–Cu distance along the c-axis within the double layers can be very short (2.5 Å), even shorter than metallic elemental copper bond (2.56 Å). The value of dρ/dT for CaCu 2-δP 2 at 300 K is approximately three times larger than in Ca 2Cu 6P 5, which suggests the likelihood of stronger electron-phonon coupling. Lastly, this study shows that the details of Cu–P layers and bonding are important for their transport characteristics. In addition, it emphasizes the remarkable character of the DOS of ‘122’ iron-based materials, despite much structural similarities.« less

  6. 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].

  7. Electron transport in dipyridazine and dipyridimine molecular junctions: a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Parashar, Sweta

    2018-05-01

    We present density functional theory-nonequilibrium Green’s function method for electron transport of dipyridazine and dipyridimine molecular junctions with gold, copper and nickel electrodes. Our investigation reveals that the junctions formed with gold and copper electrodes bridging dipyridazine molecule through thiol anchoring group enhance current as compared to the junctions in which the molecule and electrode were coupled directly. Further, nickel electrode displays weak decrease of current with increase of voltage at about 1.2 V. The result is fully rationalized by means of the distribution of molecular orbitals as well as shift in molecular energy levels and HOMO-LUMO gap with applied bias voltage. Our findings are compared with theoretical and experimental results available for other molecular junctions. Present results predict potential avenues for changing the transport behavior by not only changing the electrodes, but also the position of nitrogen atom and type of anchoring-atom that connect molecule and electrodes, thus extending applications of dipyridazine and dipyridimine molecule in future integrated circuits.

  8. 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).

  9. 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.

  10. 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.

  11. Global effect of the lack of inorganic polyphosphate in the extremophilic archaeon Sulfolobus solfataricus: A proteomic approach.

    PubMed

    Soto, Daniela F; Recalde, Alejandra; Orell, Alvaro; Albers, Sonja-Verena; Paradela, Alberto; Navarro, Claudio A; Jerez, Carlos A

    2018-03-01

    Inorganic polyphosphates (polyP) are present in all living cells and several important functions have been described for them. They are involved in the response to stress conditions, such as nutrient depletion, oxidative stress and toxic metals amongst others. A recombinant strain of Sulfolobus solfataricus unable to accumulate polyP was designed by the overexpression of its endogenous ppx gene. The overall impact of the lack of polyP on this S. solfataricus polyP (-) strain was analyzed by using quantitative proteomics (isotope-coded protein label, ICPL). Stress-related proteins, such as peroxiredoxins and heat shock proteins, proteins involved in metabolism and several others were produced at higher levels in the ppx expression strain. The polyP deficient strain showed an increased copper sensitivity and an earlier transcriptional up-regulation of copA gene coding for the P-type copper-exporting ATPase. This implies a complementary function of both copper resistance systems. These results strongly suggests that the lack of polyP makes this hyperthermophilic archaeon more sensitive to toxic conditions, such as an exposure to metals or other harmful stimuli, emphasizing the importance of this inorganic phosphate polymers in the adaptations to live in the environmental conditions in which thermoacidophilic archaea thrive. Inorganic polyphosphate (polyP) are ubiquitous molecules with many functions in living organisms. Few studies related to these polymers have been made in archaea. The construction of a polyP deficient recombinant strain of Sulfolobus solfataricus allowed the study of the global changes in the proteome of this thermoacidophilic archaeon in the absence of polyP compared with the wild type strain. The results obtained using quantitative proteomics suggest an important participation of polyP in the oxidative stress response of the cells and as having a possible metabolic role in the cell, as previously described in bacteria. The polyP deficient strain also showed an increased copper sensitivity and an earlier transcriptional up-regulation of copA, implying a complementary role of both copper resistance systems. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. 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

  13. Optoelectronic Properties of Strontium and Barium Copper Sulfides Prepared by Combinatorial Sputtering

    DOE PAGES

    Han, Yanbing; Siol, Sebastian; Zhang, Qun; ...

    2017-09-27

    Optically transparent materials with p-type electrical conductivity can facilitate the development of transparent electronics and improve the efficiency of photovoltaic solar cells. Sulfide materials represent an interesting alternative to oxides for these applications due to better hole transport properties. We prepare transparent and conductive Ba-Cu-S thin films by combinatorial cosputtering and characterized for their composition, structure, and optoelectronic properties. The conductivity and transparency of these films are found to be strongly dependent on their chemical composition and the substrate temperature during growth. The conductivity of BaCu 2S 2 and BaCu 4S 3 can reach 53 S/cm (at 250 °C) andmore » 74 S/cm (at 200 degrees C), respectively, which is higher than their solution processed/bulk counterparts. The 90% reflectance corrected transmittance is achieved in the wavelength range 600-1000 nm for BaCu 2S 2 and 650-1000 nm for BaCu 4S 3 (at 250 °C). These electrical and optical properties are comparable with other recently presented transparent p-type conductors, while the 200-350 degrees C processing temperature is low enough to be used in semiconductor devices with limited thermal budgets. Some attempts have been made to synthesize the related Sr-Cu-S materials, following the theoretical suggestion of their potential as transparent p-type conductors, but these attempts resulted only in phase-separated SrS and CuxS phases. Alloying BaCu 2S 2 with Sr on the Ba site on the other hand increases the conductivity to >100 S/cm while only slightly compromising the transparency of the material. To explain the difference between the Ba and the Sr containing copper sulfides, the lower bounds on the SrCu 2S 2 and SrCu 4S 3 formation enthalpies are estimated. While the doping of the Ba-Cu-S materials presented here is too large for application in transparent electronics, it is promising for potential use as p-type contact layers in thin film solar cells.« less

  14. Optoelectronic Properties of Strontium and Barium Copper Sulfides Prepared by Combinatorial Sputtering

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

    Han, Yanbing; Siol, Sebastian; Zhang, Qun

    Optically transparent materials with p-type electrical conductivity can facilitate the development of transparent electronics and improve the efficiency of photovoltaic solar cells. Sulfide materials represent an interesting alternative to oxides for these applications due to better hole transport properties. We prepare transparent and conductive Ba-Cu-S thin films by combinatorial cosputtering and characterized for their composition, structure, and optoelectronic properties. The conductivity and transparency of these films are found to be strongly dependent on their chemical composition and the substrate temperature during growth. The conductivity of BaCu 2S 2 and BaCu 4S 3 can reach 53 S/cm (at 250 °C) andmore » 74 S/cm (at 200 degrees C), respectively, which is higher than their solution processed/bulk counterparts. The 90% reflectance corrected transmittance is achieved in the wavelength range 600-1000 nm for BaCu 2S 2 and 650-1000 nm for BaCu 4S 3 (at 250 °C). These electrical and optical properties are comparable with other recently presented transparent p-type conductors, while the 200-350 degrees C processing temperature is low enough to be used in semiconductor devices with limited thermal budgets. Some attempts have been made to synthesize the related Sr-Cu-S materials, following the theoretical suggestion of their potential as transparent p-type conductors, but these attempts resulted only in phase-separated SrS and CuxS phases. Alloying BaCu 2S 2 with Sr on the Ba site on the other hand increases the conductivity to >100 S/cm while only slightly compromising the transparency of the material. To explain the difference between the Ba and the Sr containing copper sulfides, the lower bounds on the SrCu 2S 2 and SrCu 4S 3 formation enthalpies are estimated. While the doping of the Ba-Cu-S materials presented here is too large for application in transparent electronics, it is promising for potential use as p-type contact layers in thin film solar cells.« less

  15. 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.

  16. Widespread Distribution and Functional Specificity of the Copper Importer CcoA: Distinct Cu Uptake Routes for Bacterial Cytochrome c Oxidases

    DOE PAGES

    Khalfaoui-Hassani, Bahia; Wu, Hongjiang; Blaby-Haas, Crysten E.; ...

    2018-02-27

    ABSTRACT Cytochromecoxidases are members of the heme-copper oxidase superfamily. These enzymes have different subunits, cofactors, and primary electron acceptors, yet they all contain identical heme-copper (Cu B) binuclear centers within their catalytic subunits. The uptake and delivery pathways of the Cu Batom incorporated into this active site, where oxygen is reduced to water, are not well understood. Our previous work with the facultative phototrophic bacteriumRhodobacter capsulatusindicated that the copper atom needed for the Cu Bsite ofcbb 3-type cytochromecoxidase (cbb 3-Cox) is imported to the cytoplasm by a major facilitator superfamily-type transporter, CcoA. In this study, a comparative genomic analysis ofmore » CcoA orthologs in alphaproteobacterial genomes showed that CcoA is widespread among organisms and frequently co-occurs with cytochromecoxidases. To define the specificity of CcoA activity, we investigated its function inRhodobacter sphaeroides, a close relative ofR. capsulatusthat contains bothcbb 3- andaa 3-Cox. Phenotypic, genetic, and biochemical characterization of mutants lacking CcoA showed that in its absence, or even in the presence of its bypass suppressors, only the production ofcbb 3-Cox and not that ofaa 3-Cox was affected. We therefore concluded that CcoA is dedicated solely tocbb 3-Cox biogenesis, establishing that distinct copper uptake systems provide the Cu Batoms to the catalytic sites of these two similar cytochromecoxidases. These findings illustrate the large variety of strategies that organisms employ to ensure homeostasis and fine control of copper trafficking and delivery to the target cuproproteins under different physiological conditions. IMPORTANCEThecbb 3- andaa 3-type cytochromecoxidases belong to the widespread heme-copper oxidase superfamily. They are membrane-integral cuproproteins that catalyze oxygen reduction to water under hypoxic and normoxic growth conditions. These enzymes diverge in terms of subunit and cofactor composition, yet they all share a conserved heme-copper binuclear site within their catalytic subunit. In this study, we show that the copper atoms of the catalytic center of two similar cytochromecoxidases from this superfamily are provided by different copper uptake systems during their biogenesis. This finding illustrates different strategies by which organisms fine-tune the trafficking of copper, which is an essential but toxic micronutrient.« less

  17. Widespread Distribution and Functional Specificity of the Copper Importer CcoA: Distinct Cu Uptake Routes for Bacterial Cytochrome c Oxidases

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

    Khalfaoui-Hassani, Bahia; Wu, Hongjiang; Blaby-Haas, Crysten E.

    ABSTRACT Cytochromecoxidases are members of the heme-copper oxidase superfamily. These enzymes have different subunits, cofactors, and primary electron acceptors, yet they all contain identical heme-copper (Cu B) binuclear centers within their catalytic subunits. The uptake and delivery pathways of the Cu Batom incorporated into this active site, where oxygen is reduced to water, are not well understood. Our previous work with the facultative phototrophic bacteriumRhodobacter capsulatusindicated that the copper atom needed for the Cu Bsite ofcbb 3-type cytochromecoxidase (cbb 3-Cox) is imported to the cytoplasm by a major facilitator superfamily-type transporter, CcoA. In this study, a comparative genomic analysis ofmore » CcoA orthologs in alphaproteobacterial genomes showed that CcoA is widespread among organisms and frequently co-occurs with cytochromecoxidases. To define the specificity of CcoA activity, we investigated its function inRhodobacter sphaeroides, a close relative ofR. capsulatusthat contains bothcbb 3- andaa 3-Cox. Phenotypic, genetic, and biochemical characterization of mutants lacking CcoA showed that in its absence, or even in the presence of its bypass suppressors, only the production ofcbb 3-Cox and not that ofaa 3-Cox was affected. We therefore concluded that CcoA is dedicated solely tocbb 3-Cox biogenesis, establishing that distinct copper uptake systems provide the Cu Batoms to the catalytic sites of these two similar cytochromecoxidases. These findings illustrate the large variety of strategies that organisms employ to ensure homeostasis and fine control of copper trafficking and delivery to the target cuproproteins under different physiological conditions. IMPORTANCEThecbb 3- andaa 3-type cytochromecoxidases belong to the widespread heme-copper oxidase superfamily. They are membrane-integral cuproproteins that catalyze oxygen reduction to water under hypoxic and normoxic growth conditions. These enzymes diverge in terms of subunit and cofactor composition, yet they all share a conserved heme-copper binuclear site within their catalytic subunit. In this study, we show that the copper atoms of the catalytic center of two similar cytochromecoxidases from this superfamily are provided by different copper uptake systems during their biogenesis. This finding illustrates different strategies by which organisms fine-tune the trafficking of copper, which is an essential but toxic micronutrient.« less

  18. 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

  19. [Structure-functional organization of eukaryotic high-affinity copper importer CTR1 determines its ability to transport copper, silver and cisplatin].

    PubMed

    Skvortsov, A N; Zatulovskiĭ, E A; Puchkova, L V

    2012-01-01

    It was shown recently, that high affinity Cu(I) importer eukaryotic protein CTR1 can also transport in vitro abiogenic Ag(I) ions and anticancer drug cisplatin. At present there is no rational explanation how CTR1 can transfer platinum group, which is different by coordination properties from highly similar Cu(I) and Ag(I). To understand this phenomenon we analyzed 25 sequences of chordate CTR1 proteins, and found out conserved patterns of organization of N-terminal extracellular part of CTR1 which correspond to initial metal binding. Extracellular copper-binding motifs were qualified by their coordination properties. It was shown that relative position of Met- and His-rich copper-binding motifs in CTR1 predisposes the extracellular CTR1 part to binding of copper, silver and cisplatin. Relation between tissue-specific expression of CTR1 gene, steady-state copper concentration, and silver and platinum accumulation in organs of mice in vivo was analyzed. Significant positive but incomplete correlation exists between these variables. Basing on structural and functional peculiarities of N-terminal part of CTR1 a hypothesis of coupled transport of copper and cisplatin has been suggested, which avoids the disagreement between CTR1-mediated cisplatin transport in vitro, and irreversible binding of platinum to Met-rich peptides.

  20. Improved photoswitching response times of MoS2 field-effect transistors by stacking p-type copper phthalocyanine layer

    NASA Astrophysics Data System (ADS)

    Pak, Jinsu; Min, Misook; Cho, Kyungjune; Lien, Der-Hsien; Ahn, Geun Ho; Jang, Jingon; Yoo, Daekyoung; Chung, Seungjun; Javey, Ali; Lee, Takhee

    2016-10-01

    Photoswitching response times (rise and decay times) of a vertical organic and inorganic heterostructure with p-type copper phthalocyanine (CuPc) and n-type molybdenum disulfide (MoS2) semiconductors are investigated. By stacking a CuPc layer on MoS2 field effect transistors, better photodetection capability and fast photoswitching rise and decay phenomena are observed. Specifically, with a 2 nm-thick CuPc layer on the MoS2 channel, the photoswitching decay time decreases from 3.57 s to 0.18 s. The p-type CuPc layer, as a passivation layer, prevents the absorption of oxygen on the surface of the MoS2 channel layer, which results in a shortened photoswitching decay time because adsorbed oxygen destroys the balanced ratio of electrons and holes, leading to the interruption of recombination processes. The suggested heterostructure may deliver enhanced photodetection abilities and photoswitching characteristics for realizing ultra-thin and sensitive photodetectors.

  1. Molecular characterization of the pSinB plasmid of the arsenite oxidizing, metallotolerant Sinorhizobium sp. M14 - insight into the heavy metal resistome of sinorhizobial extrachromosomal replicons.

    PubMed

    Romaniuk, Krzysztof; Dziewit, Lukasz; Decewicz, Przemyslaw; Mielnicki, Sebastian; Radlinska, Monika; Drewniak, Lukasz

    2017-01-01

    Sinorhizobium sp. M14 is an As(III)-oxidizing, psychrotolerant strain, capable of growth in the presence of extremely high concentrations of arsenic and many other heavy metals. Metallotolerant abilities of the M14 strain depend upon the presence of two extrachromosomal replicons: pSinA (∼ 109 kb) and pSinB (∼ 300 kb). The latter was subjected to complex analysis. The performed analysis demonstrated that the plasmid pSinB is a narrow-host-range repABC-type replicon, which is fully stabilized by the phd-vapC-like toxin-antitoxin stabilizing system. In silico analysis showed that among the phenotypic gene clusters of the plasmid pSinB, eight modules are potentially involved in heavy metals resistance (HMR). These modules carry genes encoding efflux pumps, permeases, transporters and copper oxidases, which provide resistance to arsenic, cadmium, cobalt, copper, iron, mercury, nickel, silver and zinc. The functional analysis revealed that the HMR modules are active and have an effect on the minimal inhibitory concentration (MIC) values observed for the heterological host cells. The phenotype was manifested by an increase or decrease of the MICs of heavy metals and it was strain specific. The analysis of distribution of the heavy metal resistance genes, i.e. resistome, in Sinorhizobium spp. plasmids, revealed that the HMR modules are common in these replicons. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  2. Rapid recovery of dilute copper from a simulated Cu-SDS solution with low-cost steel wool cathode reactor.

    PubMed

    Chang, Shih-Hsien; Wang, Kai-Sung; Hu, Pei-I; Lui, I-Chun

    2009-04-30

    Copper-surfactant wastewaters are often encountered in electroplating, printed circuit boards manufacturing, and metal finishing industries, as well as in retentates from micellar-enhanced ultrafiltration process. A low-cost three-dimensional steel wool cathode reactor was evaluated for electrolytic recovery of Cu ion from dilute copper solution (0.2mM) in the presence of sodium dodecyl sulfate (SDS), octylphenol poly (ethyleneglycol) 9.5 ether (TX), nonylphenol poly (oxyethylene) 9 ether (NP9) and polyoxyethylene (20) sorbitan monooleate (TW) and also mixed surfactants (anionic/nonionic). The reactor showed excellent copper recovery ability in comparison to a parallel-plate reactor. The reactor rapidly recovered copper with a reasonable current efficiency. 93% of copper was recovered at current density of 1 A m(-2) and pH 4 in the presence of 8.5mM SDS. Initial solution pH, cathodic current density, solution mixing condition, SDS concentration, and initial copper concentrations significantly influenced copper recovery. The copper recovery rate increased with an increase in aqueous SDS concentrations between 5 and 8.5mM. The influences of nonionic surfactants on Cu recovery from SDS-Cu solution depended not only on the type of surfactants used, but also on applied concentrations. From the copper recovery perspective, TX at 0.1mM or NP should be selected rather than TW, because they did not inhibit copper recovery from SDS-Cu solution.

  3. 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

  4. 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.

  5. Role of an archaeal PitA transporter in the copper and arsenic resistance of Metallosphaera sedula, an extreme thermoacidophile.

    PubMed

    McCarthy, Samuel; Ai, Chenbing; Wheaton, Garrett; Tevatia, Rahul; Eckrich, Valerie; Kelly, Robert; Blum, Paul

    2014-10-01

    Thermoacidophilic archaea, such as Metallosphaera sedula, are lithoautotrophs that occupy metal-rich environments. In previous studies, an M. sedula mutant lacking the primary copper efflux transporter, CopA, became copper sensitive. In contrast, the basis for supranormal copper resistance remained unclear in the spontaneous M. sedula mutant, CuR1. Here, transcriptomic analysis of copper-shocked cultures indicated that CuR1 had a unique regulatory response to metal challenge corresponding to the upregulation of 55 genes. Genome resequencing identified 17 confirmed mutations unique to CuR1 that were likely to change gene function. Of these, 12 mapped to genes with annotated function associated with transcription, metabolism, or transport. These mutations included 7 nonsynonymous substitutions, 4 insertions, and 1 deletion. One of the insertion mutations mapped to pseudogene Msed_1517 and extended its reading frame an additional 209 amino acids. The extended mutant allele was identified as a homolog of Pho4, a family of phosphate symporters that includes the bacterial PitA proteins. Orthologs of this allele were apparent in related extremely thermoacidophilic species, suggesting M. sedula naturally lacked this gene. Phosphate transport studies combined with physiologic analysis demonstrated M. sedula PitA was a low-affinity, high-velocity secondary transporter implicated in copper resistance and arsenate sensitivity. Genetic analysis demonstrated that spontaneous arsenate-resistant mutants derived from CuR1 all underwent mutation in pitA and nonselectively became copper sensitive. Taken together, these results point to archaeal PitA as a key requirement for the increased metal resistance of strain CuR1 and its accelerated capacity for copper bioleaching. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

  6. Role of an Archaeal PitA Transporter in the Copper and Arsenic Resistance of Metallosphaera sedula, an Extreme Thermoacidophile

    PubMed Central

    McCarthy, Samuel; Ai, Chenbing; Wheaton, Garrett; Tevatia, Rahul; Eckrich, Valerie; Kelly, Robert

    2014-01-01

    Thermoacidophilic archaea, such as Metallosphaera sedula, are lithoautotrophs that occupy metal-rich environments. In previous studies, an M. sedula mutant lacking the primary copper efflux transporter, CopA, became copper sensitive. In contrast, the basis for supranormal copper resistance remained unclear in the spontaneous M. sedula mutant, CuR1. Here, transcriptomic analysis of copper-shocked cultures indicated that CuR1 had a unique regulatory response to metal challenge corresponding to the upregulation of 55 genes. Genome resequencing identified 17 confirmed mutations unique to CuR1 that were likely to change gene function. Of these, 12 mapped to genes with annotated function associated with transcription, metabolism, or transport. These mutations included 7 nonsynonymous substitutions, 4 insertions, and 1 deletion. One of the insertion mutations mapped to pseudogene Msed_1517 and extended its reading frame an additional 209 amino acids. The extended mutant allele was identified as a homolog of Pho4, a family of phosphate symporters that includes the bacterial PitA proteins. Orthologs of this allele were apparent in related extremely thermoacidophilic species, suggesting M. sedula naturally lacked this gene. Phosphate transport studies combined with physiologic analysis demonstrated M. sedula PitA was a low-affinity, high-velocity secondary transporter implicated in copper resistance and arsenate sensitivity. Genetic analysis demonstrated that spontaneous arsenate-resistant mutants derived from CuR1 all underwent mutation in pitA and nonselectively became copper sensitive. Taken together, these results point to archaeal PitA as a key requirement for the increased metal resistance of strain CuR1 and its accelerated capacity for copper bioleaching. PMID:25092032

  7. 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

  8. Sorption of copper, zinc and cobalt by oat and oat products.

    PubMed

    Górecka, Danuta; Stachowiak, Jadwiga

    2002-04-01

    We determined copper, zinc and cobalt sorption by oat and its products under variable pH conditions as well as the content of neutral dietary fiber (NDF) and its fractional composition. Adsorbents in a model sorption system were: oat, dehulled oat, oats bran and oats flakes. Three various buffers (pH 1.8, 6.6 and 8.7) were used as dispersing solutions. Results collected during this study indicate that copper, zinc and cobalt sorption is significantly affected by the type of cereal raw material. Zinc and copper ions are subjected to higher sorption than cobalt ions. Examined metal ions were subjected to high sorption under conditions corresponding to the duodenum environment (pH 8.7), regardless of the kind of adsorbent. A little lower sorption capacity is observed under conditions close to the neutral environment, while the lowest one is found in environment reflecting conditions of stomach juice (pH 1.8). Zinc ions are bound intensively by dehulled oat, while oats flakes bound mostly copper and cobalt, independently on environmental conditions. Contents of dietary fiber in oat, dehulled oat, oat bran and oat flakes were: 40.1, 19.3, 20.3 and 14.3%, respectively. The dominating fraction in all oat products was the fraction of hemicelluloses. The content of remaining fractions varies in dependence on the product.

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed Central

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

    2014-01-01

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

  11. Global Transcriptional Profiles of the Copper Responses in the Cyanobacterium Synechocystis sp. PCC 6803

    PubMed Central

    Giner-Lamia, Joaquin; López-Maury, Luis; Florencio, Francisco J.

    2014-01-01

    Copper is an essential element involved in fundamental processes like respiration and photosynthesis. However, it becomes toxic at high concentration, which has forced organisms to control its cellular concentration. We have recently described a copper resistance system in the cyanobacterium Synechocystis sp. PCC 6803, which is mediated by the two-component system, CopRS, a RND metal transport system, CopBAC and a protein of unknown function, CopM. Here, we report the transcriptional responses to copper additions at non-toxic (0.3 µM) and toxic concentrations (3 µM) in the wild type and in the copper sensitive copR mutant strain. While 0.3 µM copper slightly stimulated metabolism and promoted the exchange between cytochrome c6 and plastocyanin as soluble electron carriers, the addition of 3 µM copper catalyzed the formation of ROS, led to a general stress response and induced expression of Fe-S cluster biogenesis genes. According to this, a double mutant strain copRsufR, which expresses constitutively the sufBCDS operon, tolerated higher copper concentration than the copR mutant strain, suggesting that Fe-S clusters are direct targets of copper toxicity in Synechocystis. In addition we have also demonstrated that InrS, a nickel binding transcriptional repressor that belong to the CsoR family of transcriptional factor, was involved in heavy metal homeostasis, including copper, in Synechocystis. Finally, global gene expression analysis of the copR mutant strain suggested that CopRS only controls the expression of copMRS and copBAC operons in response to copper. PMID:25268225

  12. 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.

  13. Assessing the Influence of Copper-Nickel-Bearing Bedrock on Baseline Water Quality in Filson Creek Watershed, Northeast Minnesota

    NASA Astrophysics Data System (ADS)

    Runkel, R. L.; Jones, P. M.; Elliott, S. M.; Woodruff, L. G.

    2017-12-01

    Mining sulfide-bearing copper (Cu), nickel (Ni), and platinum-group-elements (PGE) deposits in the Duluth Complex of northeast Minnesota could have detrimental effects on surrounding water resources and associated ecosystems. A study was conducted to 1) assess copper, nickel, and other metal concentrations in surface water, bedrock, streambed sediments, and soils in watersheds where the basal part of the Duluth Complex is exposed or near the land surface; and 2) determine if these concentrations, and metal-bearing deposits, are currently influencing regional water quality in areas of potential base-metal mining. One of the watersheds that was assessed was the Filson Creek watershed, where shallow Cu-Ni-PGE deposits are present. Field water-quality, streambed sediments, soils, bedrock, and streamflow data set were collected in Filson Creek and it's watershed in 2014 and 2015. Surface-water samples were analyzed for 12 trace metals (dissolved and total concentrations), 14 inorganic constituents (dissolved concentrations), alkalinity, 18 O /16O and 2H/1H isotopes, and total and dissolved organic carbon. Background total Cu and Ni concentrations in the creek in 2014 and 2015 ranged from 1.2 to 10.8 micrograms per liter (µg/L), and 1.7 to 8.4 µg/L, respectively. The concentrations of copper, nickel, and other trace metals in surface waters and streambed sediments reflects the geochemistry of underlying rock types and glacially transported unconsolidated material, establishing baseline conditions prior to any mining. Dissolved and total organic carbon (DOC and TOC) concentrations in surface waters are very high compared to most surface waters in Minnesota, ranging from 21.3 to 43.2 milligrams per liter (mg/L), and 22.4 and 53.5 mg/L. Synoptic water-quality and flow data from a tracer test conducted over a stream segment of Filson Creek above a shallow Cu-Ni-PGE deposit (Spruce Road Deposit) was used with the 2014-15 water-quality and synthetic flow data to calibrate the reactive transport model. Results from transport modeling suggest that the high DOC content exert control on copper and other trace metal transport.

  14. Overlap of copper and iron uptake systems in mitochondria in Saccharomyces cerevisiae

    PubMed Central

    Wang, Jing; Gammon, Micah G.; Maynard, Margaret K.; White, Olivia L.; Cobine, Jai A.; Mahone, Wilkerson K.

    2016-01-01

    In Saccharomyces cerevisiae, the mitochondrial carrier family protein Pic2 imports copper into the matrix. Deletion of PIC2 causes defects in mitochondrial copper uptake and copper-dependent growth phenotypes owing to decreased cytochrome c oxidase activity. However, copper import is not completely eliminated in this mutant, so alternative transport systems must exist. Deletion of MRS3, a component of the iron import machinery, also causes a copper-dependent growth defect on non-fermentable carbon. Deletion of both PIC2 and MRS3 led to a more severe respiratory growth defect than either individual mutant. In addition, MRS3 expressed from a high copy number vector was able to suppress the oxygen consumption and copper uptake defects of a strain lacking PIC2. When expressed in Lactococcus lactis, Mrs3 mediated copper and iron import. Finally, a PIC2 and MRS3 double mutant prevented the copper-dependent activation of a heterologously expressed copper sensor in the mitochondrial intermembrane space. Taken together, these data support a role for the iron transporter Mrs3 in copper import into the mitochondrial matrix. PMID:26763345

  15. Overexpression of copper transporter CTR1 in the brain barrier of North Ronaldsay sheep: implications for the study of neurodegenerative disease.

    PubMed

    Haywood, S; Vaillant, C

    2014-01-01

    Age-related regulatory failure of the brain barrier towards the influx of redox metals such as copper and iron may be associated with the pathological changes that characterize dementias such as Alzheimer's diseases (ADs) and amyotrophic lateral sclerosis (ALS). The integrity of the brain barrier to regulate copper in the brain is maintained by the complex interplay of membrane-located transporters, of which copper transporter 1 (CTR1) exerts a defining role. North Ronaldsay (NR) sheep are a primitive breed that have adapted to a copper-deficient environment by an enhanced uptake of the metal, resulting in copper overload in the liver and brain. This study reports that CTR1 is overexpressed in both the blood-brain barrier (BBB) and the blood-cerebrospinal fluid barrier (BCB) of adult NR sheep when compared with a domesticated breed. The excess copper is stored ultimately in astrocytes as non-injurious copper-metallothionein (MT). NR sheep have apparently retained an immature regulatory setting for CTR1 in the BBB, promoting facilitated copper uptake into the brain. This putative failure of maturation of CTR1 allows insight into the regulatory control of brain copper homeostasis, whereby the BBB and BCB act in concert to sequester excess copper and protect neurons from injury. The elevated copper content of the ageing human brain may derive from a dysregulation of CTR1 at the brain barrier, with a return to the default (immature) setting and implications for neurodegenerative disease. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. COPT6 is a plasma membrane transporter that functions in copper homeostasis in Arabidopsis and is a novel target of SQUAMOSA promoter binding protein-like 7

    USDA-ARS?s Scientific Manuscript database

    Among the mechanisms controlling copper homeostasis in plants is the regulation of its uptake and tissue partitioning. Here we characterized a newly identified member of the conserved CTR/COPT family of copper transporters in Arabidopsis thaliana, COPT6. We showed that COPT6 resides at the plasma me...

  17. Unexpected role of the copper transporter ATP7A in PDGF-induced vascular smooth muscle cell migration.

    PubMed

    Ashino, Takashi; Sudhahar, Varadarajan; Urao, Norifumi; Oshikawa, Jin; Chen, Gin-Fu; Wang, Huan; Huo, Yuqing; Finney, Lydia; Vogt, Stefan; McKinney, Ronald D; Maryon, Edward B; Kaplan, Jack H; Ushio-Fukai, Masuko; Fukai, Tohru

    2010-09-17

    Copper, an essential nutrient, has been implicated in vascular remodeling and atherosclerosis with unknown mechanism. Bioavailability of intracellular copper is regulated not only by the copper importer CTR1 (copper transporter 1) but also by the copper exporter ATP7A (Menkes ATPase), whose function is achieved through copper-dependent translocation from trans-Golgi network (TGN). Platelet-derived growth factor (PDGF) promotes vascular smooth muscle cell (VSMC) migration, a key component of neointimal formation. To determine the role of copper transporter ATP7A in PDGF-induced VSMC migration. Depletion of ATP7A inhibited VSMC migration in response to PDGF or wound scratch in a CTR1/copper-dependent manner. PDGF stimulation promoted ATP7A translocation from the TGN to lipid rafts, which localized at the leading edge, where it colocalized with PDGF receptor and Rac1, in migrating VSMCs. Mechanistically, ATP7A small interfering RNA or CTR small interfering RNA prevented PDGF-induced Rac1 translocation to the leading edge, thereby inhibiting lamellipodia formation. In addition, ATP7A depletion prevented a PDGF-induced decrease in copper level and secretory copper enzyme precursor prolysyl oxidase (Pro-LOX) in lipid raft fraction, as well as PDGF-induced increase in LOX activity. In vivo, ATP7A expression was markedly increased and copper accumulation was observed by synchrotron-based x-ray fluorescence microscopy at neointimal VSMCs in wire injury model. These findings suggest that ATP7A plays an important role in copper-dependent PDGF-stimulated VSMC migration via recruiting Rac1 to lipid rafts at the leading edge, as well as regulating LOX activity. This may contribute to neointimal formation after vascular injury. Our findings provide insight into ATP7A as a novel therapeutic target for vascular remodeling and atherosclerosis.

  18. 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.

  19. Fluorinated copper phthalocyanine nanowires for enhancing interfacial electron transport in organic solar cells.

    PubMed

    Yoon, Seok Min; Lou, Sylvia J; Loser, Stephen; Smith, Jeremy; Chen, Lin X; Facchetti, Antonio; Marks, Tobin J; Marks, Tobin

    2012-12-12

    Zinc oxide is a promising candidate as an interfacial layer (IFL) in inverted organic photovoltaic (OPV) cells due to the n-type semiconducting properties as well as chemical and environmental stability. Such ZnO layers collect electrons at the transparent electrode, typically indium tin oxide (ITO). However, the significant resistivity of ZnO IFLs and an energetic mismatch between the ZnO and the ITO layers hinder optimum charge collection. Here we report that inserting nanoscopic copper hexadecafluorophthalocyanine (F(16)CuPc) layers, as thin films or nanowires, between the ITO anode and the ZnO IFL increases OPV performance by enhancing interfacial electron transport. In inverted P3HT:PC(61)BM cells, insertion of F(16)CuPc nanowires increases the short circuit current density (J(sc)) versus cells with only ZnO layers, yielding an enhanced power conversion efficiency (PCE) of ∼3.6% vs ∼3.0% for a control without the nanowire layer. Similar effects are observed for inverted PTB7:PC(71)BM cells where the PCE is increased from 8.1% to 8.6%. X-ray scattering, optical, and electrical measurements indicate that the performance enhancement is ascribable to both favorable alignment of the nanowire π-π stacking axes parallel to the photocurrent flow and to the increased interfacial layer-active layer contact area. These findings identify a promising strategy to enhance inverted OPV performance by inserting anisotropic nanostructures with π-π stacking aligned in the photocurrent flow direction.

  20. 49 CFR 192.125 - Design of copper pipe.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 3 2010-10-01 2010-10-01 false Design of copper pipe. 192.125 Section 192.125... BY PIPELINE: MINIMUM FEDERAL SAFETY STANDARDS Pipe Design § 192.125 Design of copper pipe. (a) Copper... hard drawn. (b) Copper pipe used in service lines must have wall thickness not less than that indicated...

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

    DOEpatents

    McCandless, Brian E.

    2001-06-26

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

  2. Differences in Copper Absorption and Accumulation between Copper-Exclusion and Copper-Enrichment Plants: A Comparison of Structure and Physiological Responses.

    PubMed

    Fu, Lei; Chen, Chen; Wang, Bin; Zhou, Xishi; Li, Shuhuan; Guo, Pan; Shen, Zhenguo; Wang, Guiping; Chen, Yahua

    2015-01-01

    Differences in copper (Cu) absorption and transport, physiological responses and structural characteristics between two types of Cu-resistant plants, Oenothera glazioviana (Cu-exclusion type) and Elsholtzia haichowensis (Cu-enrichment type), were investigated in the present study. The results indicated the following: (1) After 50 μM Cu treatment, the Cu ratio in the xylem vessels of E. haichowensis increased by 60%. A Cu adsorption experiment indicated that O. glazioviana exhibited greater resistance to Cu, and Cu absorption and the shoot/root ratio of Cu were significantly lower in O. glazioviana than in E. haichowensis. (2) An analysis of the endogenous abscisic acid (ABA) variance and exogenous ABA treatment demonstrated that the ABA levels of both plants did not differ; exogenous ABA treatment clearly reduced Cu accumulation in both plants. (3) The leaf stomatal density of O. glazioviana was significantly less than that of E. haichowensis. Guard cells in E. haichowensis plants were covered with a thick cuticle layer, the epidermal hair was more numerous and longer, and the number of xylem conduits in the root was small. (4) The transpiration rate and the stomatal conductance of O. glazioviana were both significantly lower than those of E. haichowensis, regardless of whether the plants were treated with Cu. Taken together, these results indicate that the differences in the structural characteristics between these two plant species, particularly in the characteristics related to plant transpiration, are important factors that govern whether plants acquire or exclude Cu.

  3. In utero copper treatment for Menkes disease associated with a severe ATP7A mutation

    PubMed Central

    Haddad, Marie Reine; Macri, Charles J.; Holmes, Courtney S.; Goldstein, David S.; Jacobson, Beryl E.; Centeno, Jose A.; Popek, Edwina J.; Gahl, Willam A.; Kaler, Stephen G.

    2012-01-01

    Menkes disease is a lethal X-linked recessive neurodegenerative disorder of copper transport caused by mutations in ATP7A, which encodes a copper-transporting ATPase. Early postnatal treatment with copper injections often improves clinical outcomes in affected infants. While Menkes disease newborns appear normal neurologically, analyses of fetal tissues including placenta indicate abnormal copper distribution and suggest a prenatal onset of the metal transport defect. In an affected fetus whose parents found termination unacceptable and who understood the associated risks, we began in utero copper histidine treatment at 31.5 weeks gestational age. Copper histidine (900 μg per dose) was administered directly to the fetus by intramuscular injection (fetal quadriceps or gluteus) under ultrasound guidance. Percutaneous umbilical blood sampling enabled serial measurement of fetal copper and ceruloplasmin levels that were used to guide therapy over a four-week period. Fetal copper levels rose from 17 μg/dL prior to treatment to 45 μg/dL, and ceruloplasmin levels from 39 mg/L to 122 mg/L. After pulmonary maturity was confirmed biochemically, the baby was delivered at 35.5 weeks and daily copper histidine therapy (250 μg sc b.i.d.) was begun. Despite this very early intervention with copper, the infant showed hypotonia, developmental delay, and electroencephalographic abnormalities and died of respiratory failure at 5.5 months of age. The patient’s ATP7A mutation, which severely disrupted mRNA splicing, resulted in complete absence of ATP7A protein on Western blots. These investigations suggest that prenatally initiated copper replacement is inadequate to correct Menkes disease caused by severe loss-of-function mutations, and that postnatal ATP7A gene addition represents a rational approach in such circumstances. PMID:22695177

  4. Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

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

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@uni.udm.ru

    2015-03-15

    Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å,more » c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.« less

  5. Mixed ternary heterojunction solar cell

    DOEpatents

    Chen, Wen S.; Stewart, John M.

    1992-08-25

    A thin film heterojunction solar cell and a method of making it has a p-type layer of mixed ternary I-III-VI.sub.2 semiconductor material in contact with an n-type layer of mixed binary II-VI semiconductor material. The p-type semiconductor material includes a low resistivity copper-rich region adjacent the back metal contact of the cell and a composition gradient providing a minority carrier mirror that improves the photovoltaic performance of the cell. The p-type semiconductor material preferably is CuInGaSe.sub.2 or CuIn(SSe).sub.2.

  6. Copper and Copper Proteins in Parkinson's Disease

    PubMed Central

    Rivera-Mancia, Susana; Diaz-Ruiz, Araceli; Tristan-Lopez, Luis; Rios, Camilo

    2014-01-01

    Copper is a transition metal that has been linked to pathological and beneficial effects in neurodegenerative diseases. In Parkinson's disease, free copper is related to increased oxidative stress, alpha-synuclein oligomerization, and Lewy body formation. Decreased copper along with increased iron has been found in substantia nigra and caudate nucleus of Parkinson's disease patients. Copper influences iron content in the brain through ferroxidase ceruloplasmin activity; therefore decreased protein-bound copper in brain may enhance iron accumulation and the associated oxidative stress. The function of other copper-binding proteins such as Cu/Zn-SOD and metallothioneins is also beneficial to prevent neurodegeneration. Copper may regulate neurotransmission since it is released after neuronal stimulus and the metal is able to modulate the function of NMDA and GABA A receptors. Some of the proteins involved in copper transport are the transporters CTR1, ATP7A, and ATP7B and the chaperone ATOX1. There is limited information about the role of those biomolecules in the pathophysiology of Parkinson's disease; for instance, it is known that CTR1 is decreased in substantia nigra pars compacta in Parkinson's disease and that a mutation in ATP7B could be associated with Parkinson's disease. Regarding copper-related therapies, copper supplementation can represent a plausible alternative, while copper chelation may even aggravate the pathology. PMID:24672633

  7. Interaction between the AAA ATPase p97/VCP and a concealed UBX domain in the copper transporter ATP7A is associated with motor neuron degeneration.

    PubMed

    Yi, Ling; Kaler, Stephen G

    2018-05-18

    The copper-transporting ATPase ATP7A contains eight transmembrane domains and is required for normal human copper homeostasis. Mutations in the ATP7A gene may lead to infantile-onset cerebral degeneration (Menkes disease); occipital horn syndrome (OHS), a related but much milder illness; or an adult-onset isolated distal motor neuropathy. The ATP7A missense mutation T994I is located in the sixth transmembrane domain of ATP7A, represents one of the variants associated with the latter phenotype, and is associated with an abnormal interaction with p97/valosin-containing protein (VCP), a hexameric AAA ATPase (ATPase associated with diverse cellular activities) with multiple biological functions. In this study, we further characterized this interaction and discovered a concealed UBX domain in the third lumenal loop of ATP7A, between its fifth and sixth transmembrane domains. We show that the T994I substitution results in conformational exposure of the UBX domain, which then binds the N-terminal domain of p97/VCP. We also show that this abnormal interaction occurs at or near the cell plasma membrane. The UBX domain has a conserved hydrophobic FP (Phe-Pro) motif, and substitution with di-alanine abrogated the interaction and restored the proper intracellular localization of ATP7A in the trans -Golgi network. Using protein MS, we identified potential coordinating components of the ATP7A T994I -p97 complex, including NSFL1 cofactor (NSF1C or p47) that may be relevant to the pathophysiology and clinical effects associated with ATP7A T994I Our study represents the first report of p97/VCP binding to a UBX domain that is not normally exposed, resulting in an aberrant protein-protein interaction leading to motor neuron degeneration.

  8. 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.

  9. 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

  10. The copper-transporting ATPase pump and its potential role in copper-tolerance

    Treesearch

    Katie Ohno; C.A. Clausen; Frederick Green; G. Stanosz

    2016-01-01

    Copper-tolerant brown-rot decay fungi exploit intricate mechanisms to neutralize the efficacy of copper-containing preservative formulations. The production and accumulation oxalate is the most widely recognized theory regarding the mechanism of copper-tolerance in these fungi. The role of oxalate, however, may be only one part of a series of necessary components...

  11. In Vivo Tracking of Copper-64 Radiolabeled Nanoparticles in Lactuca sativa.

    PubMed

    Davis, Ryan A; Rippner, Devin A; Hausner, Sven H; Parikh, Sanjai J; McElrone, Andrew J; Sutcliffe, Julie L

    2017-11-07

    Engineered nanoparticles (NPs) are increasingly used in commercial products including automotive lubricants, clothing, deodorants, sunscreens, and cosmetics and can potentially accumulate in our food supply. Given their size it is difficult to detect and visualize the presence of NPs in environmental samples, including crop plants. New analytical tools are needed to fill the void for detection and visualization of NPs in complex biological and environmental matrices. We aimed to determine whether radiolabeled NPs could be used as a noninvasive, highly sensitive analytical tool to quantitatively track and visualize NP transport and accumulation in vivo in lettuce (Lactuca sativa) and to investigate the effect of NP size on transport and distribution over time using a combination of autoradiography, positron emission tomography (PET)/computed tomography (CT), scanning electron microscopy (SEM), and transition electron microscopy (TEM). Azide functionalized NPs were radiolabeled via a "click" reaction with copper-64 ( 64 Cu)-1,4,7-triazacyclononane triacetic acid (NOTA) azadibenzocyclooctyne (ADIBO) conjugate ([ 64 Cu]-ADIBO-NOTA) via copper-free Huisgen-1,3-dipolar cycloaddition reaction. This yielded radiolabeled [ 64 Cu]-NPs of uniform shape and size with a high radiochemical purity (>99%), specific activity of  2.2 mCi/mg of NP, and high stability (i.e., no detectable dissolution) over 24 h across a pH range of 5-9. Both PET/CT and autoradiography showed that [ 64 Cu]-NPs entered the lettuce seedling roots and were rapidly transported to the cotyledons with the majority of the accumulation inside the roots. Uptake and transport of intact NPs was size-dependent, and in combination with the accumulation within the roots suggests a filtering effect of the plant cell walls at various points along the water transport pathway.

  12. Evaluation of Wood Species and Preservatives for Use in Wisconsin Highway Sign Posts

    Treesearch

    Stan T. Lebow; Robert J. Ross; Samuel L. Zelinka

    2014-01-01

    The Wisconsin Department of Transportation (WisDOT) uses wooden posts to support many types of signs along state highways. WisDOT currently uses red pine or Southern Pine posts treated with chromated copper arsenate (CCA) and has generally experienced satisfactory performance and service life. However, there are some areas of concern, as well as potential opportunities...

  13. Placenta Copper Transport Proteins in Preeclampsia

    USDA-ARS?s Scientific Manuscript database

    Placental insufficiency underlying preeclampsia (PE) is associated with impaired placental angiogenesis. As copper (Cu) is essential to angiogenesis, we investigated differences in the expression of placental Cu transporters Menkes (ATP7A), Wilsons (ATP7B) and the Cu chaperone (CCS) for superoxide d...

  14. Freestanding three-dimensional core–shell nanoarrays for lithium-ion battery anodes

    DOE PAGES

    Tan, Guoqiang; Wu, Feng; Yuan, Yifei; ...

    2016-06-03

    Here, structural degradation and low conductivity of transition-metal oxides lead to severe capacity fading in lithium-ion batteries. Recent efforts to solve this issue have mainly focused on using nanocomposites or hybrids by integrating nanosized metal oxides with conducting additives. Here we design specific hierarchical structures and demonstrate their use in flexible, large-area anode assemblies. Fabrication of these anodes is achieved via oxidative growth of copper oxide nanowires onto copper substrates followed by radio-frequency sputtering of carbon-nitride films, forming freestanding three-dimensional arrays with core–shell nano-architecture. Cable-like copper oxide/carbon-nitride core–shell nanostructures accommodate the volume change during lithiation-delithiation processes, the three-dimensional arrays providemore » abundant electroactive zones and electron/ion transport paths, and the monolithic sandwich-type configuration without additional binders or conductive agents improves energy/power densities of the whole electrode.« less

  15. Freestanding three-dimensional core-shell nanoarrays for lithium-ion battery anodes.

    PubMed

    Tan, Guoqiang; Wu, Feng; Yuan, Yifei; Chen, Renjie; Zhao, Teng; Yao, Ying; Qian, Ji; Liu, Jianrui; Ye, Yusheng; Shahbazian-Yassar, Reza; Lu, Jun; Amine, Khalil

    2016-06-03

    Structural degradation and low conductivity of transition-metal oxides lead to severe capacity fading in lithium-ion batteries. Recent efforts to solve this issue have mainly focused on using nanocomposites or hybrids by integrating nanosized metal oxides with conducting additives. Here we design specific hierarchical structures and demonstrate their use in flexible, large-area anode assemblies. Fabrication of these anodes is achieved via oxidative growth of copper oxide nanowires onto copper substrates followed by radio-frequency sputtering of carbon-nitride films, forming freestanding three-dimensional arrays with core-shell nano-architecture. Cable-like copper oxide/carbon-nitride core-shell nanostructures accommodate the volume change during lithiation-delithiation processes, the three-dimensional arrays provide abundant electroactive zones and electron/ion transport paths, and the monolithic sandwich-type configuration without additional binders or conductive agents improves energy/power densities of the whole electrode.

  16. Temporal aspects of copper homeostasis and its crosstalk with hormones

    PubMed Central

    Peñarrubia, Lola; Romero, Paco; Carrió-Seguí, Angela; Andrés-Bordería, Amparo; Moreno, Joaquín; Sanz, Amparo

    2015-01-01

    To cope with the dual nature of copper as being essential and toxic for cells, plants temporarily adapt the expression of copper homeostasis components to assure its delivery to cuproproteins while avoiding the interference of potential oxidative damage derived from both copper uptake and photosynthetic reactions during light hours. The circadian clock participates in the temporal organization of coordination of plant nutrition adapting metabolic responses to the daily oscillations. This timely control improves plant fitness and reproduction and holds biotechnological potential to drive increased crop yields. Hormonal pathways, including those of abscisic acid, gibberellins, ethylene, auxins, and jasmonates are also under direct clock and light control, both in mono and dicotyledons. In this review, we focus on copper transport in Arabidopsis thaliana and Oryza sativa and the presumable role of hormones in metal homeostasis matching nutrient availability to growth requirements and preventing metal toxicity. The presence of putative hormone-dependent regulatory elements in the promoters of copper transporters genes suggests hormonal regulation to match special copper requirements during plant development. Spatial and temporal processes that can be affected by hormones include the regulation of copper uptake into roots, intracellular trafficking and compartmentalization, and long-distance transport to developing vegetative and reproductive tissues. In turn, hormone biosynthesis and signaling are also influenced by copper availability, which suggests reciprocal regulation subjected to temporal control by the central oscillator of the circadian clock. This transcriptional regulatory network, coordinates environmental and hormonal signaling with developmental pathways to allow enhanced micronutrient acquisition efficiency. PMID:25941529

  17. 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.

  18. 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

  19. Effect of dietary copper and breed on gene products involved in copper acquisition, distribution, and use in Angus and Simmental cows and fetuses.

    PubMed

    Fry, R S; Spears, J W; Lloyd, K E; O'Nan, A T; Ashwell, M S

    2013-02-01

    Copper (Cu) deficiency is a widespread problem in cattle across the United States and breed differences in Cu metabolism may contribute to this issue. Intracellular Cu is tightly regulated by transport and chaperone proteins, and to date, these mechanisms have not been elucidated to address breed differences in Cu metabolism, nor have these proteins been characterized in bovine fetal liver. Mature, pregnant Angus (n = 8) and Simmental (n = 8) cows (∼4 mo into gestation) were used in a 2 × 2 factorial arrangement of treatments. All cows were bred to Angus sires resulting in an Angus vs. Simmental × Angus comparison for fetuses. Cows were randomly assigned to corn silage-based diets that were either adequate (+Cu) or deficient (-Cu; 6.6 mg Cu/kg DM) in Cu. Diets were individually fed for 112 d. At the end of the study, cows were harvested to collect duodenal mucosa scrapes, liver samples, and fetal liver samples for mineral analysis and also for mRNA and protein analysis of Cu transport and chaperone proteins. Placentomes were also obtained for mineral analysis. Plasma Cu and liver Cu were affected by Cu, breed, and Cu × breed. Both of these Cu indices were less (P ≤ 0.05) in-Cu Simmentals (-CuS) than in-Cu Angus (- uA), but were similar among +Cu Simmental (+CuS) and +Cu Angus cows (+CuA). Duodenal Cu was less (P = 0.01) in-Cu vs. +Cu cows. Placentome Cu was less (P = 0.003) in-Cu vs. +Cu cows, and was also less (P = 0.03) in Simmentals vs. Angus. Fetal liver Cu was less (P = 0.002) in-Cu vs. +Cu fetuses, and was also less (P = 0.05) in Simmental × Angus vs. Angus. Abundance of Cu transporter1 (CTR1) protein and transcripts for Cu transporters and chaperones were not affected by Cu or breed in liver and were not affected by Cu in the intestine. Duodenal Ctr1 was less (P = 0.04) and CTR1 tended (P = 0.10) to be less in Simmentals vs. Angus. Expression of Atp7a tended (P = 0.08) to be less in Simmentals than in Angus. In fetal liver, expression of antioxidant 1 (Atox1), cytochrome c oxidase assembly protein 17 (Cox17), and Cu metabolism MURR1 domain 1 (Commd1) were up-regulated (P ≤ 0.05) in-Cu vs. +Cu fetuses. In conclusion, less expression of duodenal Ctr1 and a tendency for less CTR1 (P = 0.10) and Atp7a (P = 0.08) suggest that Simmentals have a lesser ability to absorb and utilize dietary Cu, and may explain why Simmentals are more prone to Cu deficiency than Angus. Up-regulation of fetal liver Atox1, Cox17, and Commd1 in-Cu fetuses may reflect the great Cu demand by the fetus.

  20. The interactome of the copper transporter ATP7A belongs to a network of neurodevelopmental and neurodegeneration factors

    PubMed Central

    Comstra, Heather S; McArthy, Jacob; Rudin-Rush, Samantha; Hartwig, Cortnie; Gokhale, Avanti; Zlatic, Stephanie A; Blackburn, Jessica B; Werner, Erica; Petris, Michael; D’Souza, Priya; Panuwet, Parinya; Barr, Dana Boyd; Lupashin, Vladimir; Vrailas-Mortimer, Alysia; Faundez, Victor

    2017-01-01

    Genetic and environmental factors, such as metals, interact to determine neurological traits. We reasoned that interactomes of molecules handling metals in neurons should include novel metal homeostasis pathways. We focused on copper and its transporter ATP7A because ATP7A null mutations cause neurodegeneration. We performed ATP7A immunoaffinity chromatography and identified 541 proteins co-isolating with ATP7A. The ATP7A interactome concentrated gene products implicated in neurodegeneration and neurodevelopmental disorders, including subunits of the Golgi-localized conserved oligomeric Golgi (COG) complex. COG null cells possess altered content and subcellular localization of ATP7A and CTR1 (SLC31A1), the transporter required for copper uptake, as well as decreased total cellular copper, and impaired copper-dependent metabolic responses. Changes in the expression of ATP7A and COG subunits in Drosophila neurons altered synapse development in larvae and copper-induced mortality of adult flies. We conclude that the ATP7A interactome encompasses a novel COG-dependent mechanism to specify neuronal development and survival. DOI: http://dx.doi.org/10.7554/eLife.24722.001 PMID:28355134

  1. Impaired copper and iron metabolism in blood cells and muscles of patients affected by copper deficiency myeloneuropathy.

    PubMed

    Spinazzi, Marco; Sghirlanzoni, Angelo; Salviati, Leonardo; Angelini, Corrado

    2014-12-01

    Severe copper deficiency leads in humans to a treatable multisystem disease characterized by anaemia and degeneration of spinal cord and nerves, but its mechanisms have not been investigated. We tested whether copper deficit leads to alterations in fundamental copper-dependent proteins and in iron metabolism in blood and muscles of patients affected by copper deficiency myeloneuropathy, and if these metabolic abnormalities are associated with compensatory mechanisms for copper maintenance. We evaluated the expression of critical copper enzymes, of iron-related proteins, and copper chaperones and transporters in blood and muscles from five copper-deficient patients presenting with subacute sensory ataxia, muscle paralysis, liver steatosis and variable anaemia. Severe copper deficiency was caused by chronic zinc intoxication in all of the patients, with an additional history of gastrectomy in two cases. The antioxidant enzyme SOD1 and subunit 2 of cytochrome c oxidase were significantly decreased in blood cells and in muscles of copper-deficient patients compared with controls. In muscle, the iron storage protein ferritin was dramatically reduced despite normal serum ferritin, and the expression of the haem-proteins cytochrome c and myoglobin was impaired. Muscle expression of the copper transporter CTR1 and of the copper chaperone CCS, was strikingly increased, while antioxidant protein 1 was diminished. copper-dependent enzymes with critical functions in antioxidant defences, in mitochondrial energy production, and in iron metabolism are affected in blood and muscles of patients with profound copper deficiency leading to myeloneuropathy. Homeostatic mechanisms are strongly activated to increase intracellular copper retention. © 2013 British Neuropathological Society.

  2. Graphene-based copper oxide thin film nanostructures as high-efficiency photocathode for p-type dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Kilic, Bayram; Turkdogan, Sunay; Astam, Aykut; Baran, Sümeyra Seniha; Asgin, Mansur; Cebeci, Hulya; Urk, Deniz

    2017-10-01

    Graphene-based p-type dye-sensitized solar cells (p-DSSCs) have been proposed and fabricated using copper oxide urchin-like nanostructures (COUN) as photocathode with an FeS2 counter electrode (CE). COUN composed of Cu2O core sphere and CuO shell nanorods with overall diameters of 2 to 4 μm were grown by a simple hydrothermal method with self-assemble nucleation. It was figured out that the formation of copper oxide core/shell structures could be adjusted by an ammonia additive leading to pH change of the precursor solution. In addition to a photocathode, we also demonstrated FeS2 thin films as an efficient CE material alternative to the conventional Pt CEs in DSSCs. FeS2 nanostructures, with diameters of 50 to 80 nm, were synthesized by a similar hydrothermal approach. FeS2 nanostructures are demonstrated to be an outstanding CE material in p-DSSCs. We report graphene/COUN as photocathode and Pt/FeS2 as CE in p-DSSCs, and results show that the synergetic combination of electrodes in each side (increased interconnectivity between COUN and graphene layer, high surface area, and high catalytic activity of FeS2) increased the power conversion efficiency from 1.56% to 3.14%. The excellent performances of COUN and FeS2 thin film in working and CEs, respectively, make them unique choices among the various photocathode and CE materials studied.

  3. Field Effect Transistors Using Atomically Thin Layers of Copper Indium Selenide (CuInSe)

    NASA Astrophysics Data System (ADS)

    Patil, Prasanna; Ghosh, Sujoy; Wasala, Milinda; Lei, Sidong; Vajtai, Robert; Ajayan, Pulickel; Talapatra, Saikat

    We will report fabrication of field-effect transistors (FETs) using few-layers of Copper Indium Selenide (CuInSe) flakes exfoliated from crystals grown using chemical vapor transport technique. Our transport measurements indicate n-type FET with electron mobility µ ~ 3 cm2 V-1 s-1 at room temperature when Silicon dioxide (SiO2) is used as a back gate. Mobility can be further increased significantly when ionic liquid 1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) is used as top gate. Similarly subthreshold swing can be further improved from 103 V/dec to 0.55 V/dec by using ionic liquid as a top gate. We also found ON/OFF ratio of ~ 102 for both top and back gate. Comparison between ionic liquid top gate and SiO2 back gate will be presented and discussed. This work is supported by the U.S. Army Research Office through a MURI Grant # W911NF-11-1-0362.

  4. Transport performance of a HTS current lead prepared by the TFA-MOD processed YBCO tapes

    NASA Astrophysics Data System (ADS)

    Shiohara, K.; Sakai, S.; Ohki, S.; Yamada, Y.; Tachikawa, K.; Koizumi, T.; Aoki, Y.; Hikichi, Y.; Nishioka, J.; Hasegawa, T.

    2009-10-01

    A superconducting current lead has been prepared using 12 tapes of the trifluoroacetates - metal organic deposition (TFA-MOD) processed Y 1Ba 2Cu 3O 7-δ (YBCO) coated conductors with critical current ( I c) of about 100 A at 77 K in self-field. The tapes are 4.5 mm in width, 220 mm in length and about 120 μm in overall thickness. The 1 μm thick superconducting YBCO layer was formed through the TFA-MOD process on Hastelloy TM substrate tapes with two buffer oxide layers of Gd 2Zr 2O 7 (GZO) and CeO 2. The 12 YBCO tapes were arrayed on the both sides (six tapes on each side) of a stainless steel board with 3 mm in thickness for a board type shape. They were similarly soldered to copper caps at the both ends. The transport current of 1000 A was stably applied for 10 min in the liquid nitrogen temperature without any voltage generation in all tapes. Although some voltage in some YBCO tapes generated at the applied currents of about 1100 A, the transport current of 1200 A was successfully applied without quenching. The voltage between both copper caps linearly increased with increasing the transport current, and it was about 300 μV at an applied current of 1000 A. A low joint resistance between the YBCO tapes and the copper caps resulted in small amounts of the Joule heating at the joints when 1000 A was applied. The overall (effective) thermal conductivity of the current leads composed of YBCO tapes and the stainless steel board was much lower than that of Non-superconducting current leads. Therefore, the present current leads with small heat leakage seemed to be practically promising for superconducting magnets.

  5. 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.

  6. Differences in Copper Absorption and Accumulation between Copper-Exclusion and Copper-Enrichment Plants: A Comparison of Structure and Physiological Responses

    PubMed Central

    Fu, Lei; Chen, Chen; Wang, Bin; Zhou, Xishi; Li, Shuhuan; Guo, Pan; Shen, Zhenguo; Wang, Guiping; Chen, Yahua

    2015-01-01

    Differences in copper (Cu) absorption and transport, physiological responses and structural characteristics between two types of Cu-resistant plants, Oenothera glazioviana (Cu-exclusion type) and Elsholtzia haichowensis (Cu-enrichment type), were investigated in the present study. The results indicated the following: (1) After 50 μM Cu treatment, the Cu ratio in the xylem vessels of E. haichowensis increased by 60%. A Cu adsorption experiment indicated that O. glazioviana exhibited greater resistance to Cu, and Cu absorption and the shoot/root ratio of Cu were significantly lower in O. glazioviana than in E. haichowensis. (2) An analysis of the endogenous abscisic acid (ABA) variance and exogenous ABA treatment demonstrated that the ABA levels of both plants did not differ; exogenous ABA treatment clearly reduced Cu accumulation in both plants. (3) The leaf stomatal density of O. glazioviana was significantly less than that of E. haichowensis. Guard cells in E. haichowensis plants were covered with a thick cuticle layer, the epidermal hair was more numerous and longer, and the number of xylem conduits in the root was small. (4) The transpiration rate and the stomatal conductance of O. glazioviana were both significantly lower than those of E. haichowensis, regardless of whether the plants were treated with Cu. Taken together, these results indicate that the differences in the structural characteristics between these two plant species, particularly in the characteristics related to plant transpiration, are important factors that govern whether plants acquire or exclude Cu. PMID:26207743

  7. Effects of Dietary Copper and Zinc Supplementation on Growth Performance, Tissue Mineral Retention, Antioxidant Status, and Fur Quality in Growing-Furring Blue Foxes (Alopex lagopus).

    PubMed

    Liu, Zhi; Wu, Xuezhuang; Zhang, Tietao; Guo, Jungang; Gao, Xiuhua; Yang, Fuhe; Xing, Xiumei

    2015-12-01

    A 4×2 factorial experiment with four supplemental levels of copper (0, 20, 40, or 60 mg copper per kg dry matter) from copper sulfate and two supplemental levels of zinc (40 or 200 mg zinc per kg dry matter) from zinc sulfate was conducted to investigate the effects of dietary copper and zinc supplementation on growth performance, tissue mineral retention, antioxidant status, and fur quality in growing-furring blue foxes. One hundred and twenty healthy 15-week-old male blue foxes were randomly allocated to eight dietary treatments with 15 replicates per treatment for a 70-day trial from mid-September to pelting in December. The average daily gain and feed conversion ratio were increased with copper supplementation in the first 35 days as well as the overall period (P<0.05). In addition, copper supplementation tended to increase feed intake during the first 35 days (P<0.10). Diets supplemented with 200 mg/kg zinc did not affect body gain (P>0.10) and feed intake (P>0.10) but improved feed conversion (P<0.05) compared with those supplemented 40 mg/kg zinc throughout the experiment. No copper×zinc interaction was observed for growth performance except that a tendency (P=0.09) was found for feed intake in the first 35 days. Supplementation of copper or zinc improved crude fat digestibility (P<0.01) but had no effects on the digestibility of other nutrients. Fecal copper was increased with both copper (P<0.01) and zinc addition (P<0.05). However, fecal zinc was affected only by dietary zinc addition (P<0.01). Mineral contents in serum and kidney were not affected by dietary treatments (P>0.05). However, the level of copper in the liver was increased with copper supplementation (P<0.05) and tended to decrease with zinc supplementation (P=0.08). Dietary zinc addition tended to increase the activity of alkaline phosphatase (P=0.07). The activities of copper-zinc superoxide dismutase and catalase tended to increase by copper (P=0.08) and zinc addition (P=0.05). Moreover, a copper×zinc interaction was observed for catalase in the experiment (P<0.05). Serum malondialdehyde concentration decreased with the increasing of dietary copper and zinc levels (P<0.05). The activity of glutathione peroxidase tended to increase by copper addition (P=0.09). For fur quality, foxes fed diets supplemented with high copper had larger skin length and darker pelts than those fed the basal diet without copper addition (P<0.05). In conclusion, this study demonstrated that dietary copper and zinc supplementation can improve growth by increasing feed intake and improving fat digestibility. Additionally, copper and zinc can enhance the antioxidant capacity of blue foxes. This study also indicates that additional zinc up to 200 mg/kg did not exert significant adverse effects on the copper metabolism of growing-furring blue foxes.

  8. [Effects of bio-crust on soil microbial biomass and enzyme activities in copper mine tailings].

    PubMed

    Chen, Zheng; Yang, Gui-de; Sun, Qing-ye

    2009-09-01

    Bio-crust is the initial stage of natural primary succession in copper mine tailings. With the Yangshanchong and Tongguanshan copper mine tailings in Tongling City of Anhui Province as test objects, this paper studied the soil microbial biomass C and N and the activities of dehydrogenase, catalase, alkaline phosphatase, and urease under different types of bio-crust. The bio-crusts improved the soil microbial biomass and enzyme activities in the upper layer of the tailings markedly. Algal crust had the best effect in improving soil microbial biomass C and N, followed by moss-algal crust, and moss crust. Soil microflora also varied with the type of bio-crust. No'significant difference was observed in the soil enzyme activities under the three types of bio-crust. Soil alkaline phosphatase activity was significantly positively correlated with soil microbial biomass and dehydrogenase and urease activities, but negatively correlated with soil pH. In addition, moss rhizoid could markedly enhance the soil microbial biomass and enzyme activities in moss crust rhizoid.

  9. Laser ablation inductively coupled plasma mass spectrometry imaging of metals in experimental and clinical Wilson's disease

    PubMed Central

    Boaru, Sorina Georgiana; Merle, Uta; Uerlings, Ricarda; Zimmermann, Astrid; Flechtenmacher, Christa; Willheim, Claudia; Eder, Elisabeth; Ferenci, Peter; Stremmel, Wolfgang; Weiskirchen, Ralf

    2015-01-01

    Wilson's disease is an autosomal recessive disorder in which the liver does not properly release copper into bile, resulting in prominent copper accumulation in various tissues. Affected patients suffer from hepatic disorders and severe neurological defects. Experimental studies in mutant mice in which the copper-transporting ATPase gene (Atp7b) is disrupted revealed a drastic, time-dependent accumulation of hepatic copper that is accompanied by formation of regenerative nodes resembling cirrhosis. Therefore, these mice represent an excellent exploratory model for Wilson's disease. However, the precise time course in hepatic copper accumulation and its impact on other trace metals within the liver is yet poorly understood. We have recently established novel laser ablation inductively coupled plasma mass spectrometry protocols allowing quantitative metal imaging in human and murine liver tissue with high sensitivity, spatial resolution, specificity and quantification ability. By use of these techniques, we here aimed to comparatively analyse hepatic metal content in wild-type and Atp7b deficient mice during ageing. We demonstrate that the age-dependent accumulation of hepatic copper is strictly associated with a simultaneous increase in iron and zinc, while the intrahepatic concentration and distribution of other metals or metalloids is not affected. The same findings were obtained in well-defined human liver samples that were obtained from patients suffering from Wilson's disease. We conclude that in Wilson's disease the imbalances of hepatic copper during ageing are closely correlated with alterations in intrahepatic iron and zinc content. PMID:25704483

  10. Copper Oxide Nanoparticles Impact Several Toxicological Endpoints and Cause Neurodegeneration in Caenorhabditis elegans

    PubMed Central

    Zanon, Tyler; Kappell, Anthony D.; Petrella, Lisa N.; Andersen, Erik C.; Hristova, Krassimira R.

    2016-01-01

    Engineered nanoparticles are becoming increasingly incorporated into technology and consumer products. In 2014, over 300 tons of copper oxide nanoparticles were manufactured in the United States. The increased production of nanoparticles raises concerns regarding the potential introduction into the environment or human exposure. Copper oxide nanoparticles commonly release copper ions into solutions, which contribute to their toxicity. We quantified the inhibitory effects of both copper oxide nanoparticles and copper sulfate on C. elegans toxicological endpoints to elucidate their biological effects. Several toxicological endpoints were analyzed in C. elegans, including nematode reproduction, feeding behavior, and average body length. We examined three wild C. elegans isolates together with the Bristol N2 laboratory strain to explore the influence of different genotypic backgrounds on the physiological response to copper challenge. All strains exhibited greater sensitivity to copper oxide nanoparticles compared to copper sulfate, as indicated by reduction of average body length and feeding behavior. Reproduction was significantly reduced only at the highest copper dose, though still more pronounced with copper oxide nanoparticles compared to copper sulfate treatment. Furthermore, we investigated the effects of copper oxide nanoparticles and copper sulfate on neurons, cells with known vulnerability to heavy metal toxicity. Degeneration of dopaminergic neurons was observed in up to 10% of the population after copper oxide nanoparticle exposure. Additionally, mutants in the divalent-metal transporters, smf-1 or smf-2, showed increased tolerance to copper exposure, implicating both transporters in copper-induced neurodegeneration. These results highlight the complex nature of CuO nanoparticle toxicity, in which a nanoparticle-specific effect was observed in some traits (average body length, feeding behavior) and a copper ion specific effect was observed for other traits (neurodegeneration, response to stress). PMID:27911941

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

    Inglese, Alessandro, E-mail: alessandro.inglese@aalto.fi; Savin, Hele; Lindroos, Jeanette

    Copper is a harmful metal impurity that significantly impacts the performance of silicon-based devices if present in active regions. In this contribution, we propose a fast method consisting of simultaneous illumination and annealing for the detection of copper contamination in p-type silicon. Our results show that, within minutes, such method is capable of producing a significant reduction of the minority carrier lifetime. A spatial distribution map of copper contamination can then be obtained through the lifetime values measured before and after degradation. In order to separate the effect of the light-activated copper defects from the other metastable complexes in lowmore » resistivity Cz-silicon, we carried out a dark anneal at 200 °C, which is known to fully recover the boron-oxygen defect. Similar to the boron-oxygen behavior, we show that the dark anneal also recovers the copper defects. However, the recovery is only partial and it can be used to identify the possible presence of copper contamination.« less

  12. Association between the Type of Workplace and Lung Function in Copper Miners

    PubMed Central

    Gruszczyński, Leszek; Wojakowska, Anna; Ścieszka, Marek; Turczyn, Barbara; Schmidt, Edward

    2016-01-01

    The aim of the analysis was to retrospectively assess changes in lung function in copper miners depending on the type of workplace. In the groups of 225 operators, 188 welders, and 475 representatives of other jobs, spirometry was performed at the start of employment and subsequently after 10, 20, and 25 years of work. Spirometry Longitudinal Data Analysis software was used to estimate changes in group means for FEV1 and FVC. Multiple linear regression analysis was used to assess an association between workplace and lung function. Lung function assessed on the basis of calculation of longitudinal FEV1 (FVC) decline was similar in all studied groups. However, multiple linear regression model used in cross-sectional analysis revealed an association between workplace and lung function. In the group of welders, FEF75 was lower in comparison to operators and other miners as early as after 10 years of work. Simultaneously, in smoking welders, the FEV1/FVC ratio was lower than in nonsmokers (p < 0,05). The interactions between type of workplace and smoking (p < 0,05) in their effect on FVC, FEV1, PEF, and FEF50 were shown. Among underground working copper miners, the group of smoking welders is especially threatened by impairment of lung ventilatory function. PMID:27274987

  13. Gene duplication and neo-functionalization in the evolutionary and functional divergence of the metazoan copper transporters Ctr1 and Ctr2.

    PubMed

    Logeman, Brandon L; Wood, L Kent; Lee, Jaekwon; Thiele, Dennis J

    2017-07-07

    Copper is an essential element for proper organismal development and is involved in a range of processes, including oxidative phosphorylation, neuropeptide biogenesis, and connective tissue maturation. The copper transporter (Ctr) family of integral membrane proteins is ubiquitously found in eukaryotes and mediates the high-affinity transport of Cu + across both the plasma membrane and endomembranes. Although mammalian Ctr1 functions as a Cu + transporter for Cu acquisition and is essential for embryonic development, a homologous protein, Ctr2, has been proposed to function as a low-affinity Cu transporter, a lysosomal Cu exporter, or a regulator of Ctr1 activity, but its functional and evolutionary relationship to Ctr1 is unclear. Here we report a biochemical, genetic, and phylogenetic comparison of metazoan Ctr1 and Ctr2, suggesting that Ctr2 arose over 550 million years ago as a result of a gene duplication event followed by loss of Cu + transport activity. Using a random mutagenesis and growth selection approach, we identified amino acid substitutions in human and mouse Ctr2 proteins that support copper-dependent growth in yeast and enhance copper accumulation in Ctr1 -/- mouse embryonic fibroblasts. These mutations revert Ctr2 to a more ancestral Ctr1-like state while maintaining endogenous functions, such as stimulating Ctr1 cleavage. We suggest key structural aspects of metazoan Ctr1 and Ctr2 that discriminate between their biological roles, providing mechanistic insights into the evolutionary, biochemical, and functional relationships between these two related proteins. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  14. 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.

  15. A Strong Loss-of-Function Mutation in RAN1 Results in Constitutive Activation of the Ethylene Response Pathway as Well as a Rosette-Lethal Phenotype

    PubMed Central

    Woeste, Keith E.; Kieber, Joseph J.

    2000-01-01

    A recessive mutation was identified that constitutively activated the ethylene response pathway in Arabidopsis and resulted in a rosette-lethal phenotype. Positional cloning of the gene corresponding to this mutation revealed that it was allelic to responsive to antagonist1 (ran1), a mutation that causes seedlings to respond in a positive manner to what is normally a competitive inhibitor of ethylene binding. In contrast to the previously identified ran1-1 and ran1-2 alleles that are morphologically indistinguishable from wild-type plants, this ran1-3 allele results in a rosette-lethal phenotype. The predicted protein encoded by the RAN1 gene is similar to the Wilson and Menkes disease proteins and yeast Ccc2 protein, which are integral membrane cation-transporting P-type ATPases involved in copper trafficking. Genetic epistasis analysis indicated that RAN1 acts upstream of mutations in the ethylene receptor gene family. However, the rosette-lethal phenotype of ran1-3 was not suppressed by ethylene-insensitive mutants, suggesting that this mutation also affects a non-ethylene-dependent pathway regulating cell expansion. The phenotype of ran1-3 mutants is similar to loss-of-function ethylene receptor mutants, suggesting that RAN1 may be required to form functional ethylene receptors. Furthermore, these results suggest that copper is required not only for ethylene binding but also for the signaling function of the ethylene receptors. PMID:10715329

  16. A strong loss-of-function mutation in RAN1 results in constitutive activation of the ethylene response pathway as well as a rosette-lethal phenotype

    NASA Technical Reports Server (NTRS)

    Woeste, K. E.; Kieber, J. J.; Evans, M. L. (Principal Investigator)

    2000-01-01

    A recessive mutation was identified that constitutively activated the ethylene response pathway in Arabidopsis and resulted in a rosette-lethal phenotype. Positional cloning of the gene corresponding to this mutation revealed that it was allelic to responsive to antagonist1 (ran1), a mutation that causes seedlings to respond in a positive manner to what is normally a competitive inhibitor of ethylene binding. In contrast to the previously identified ran1-1 and ran1-2 alleles that are morphologically indistinguishable from wild-type plants, this ran1-3 allele results in a rosette-lethal phenotype. The predicted protein encoded by the RAN1 gene is similar to the Wilson and Menkes disease proteins and yeast Ccc2 protein, which are integral membrane cation-transporting P-type ATPases involved in copper trafficking. Genetic epistasis analysis indicated that RAN1 acts upstream of mutations in the ethylene receptor gene family. However, the rosette-lethal phenotype of ran1-3 was not suppressed by ethylene-insensitive mutants, suggesting that this mutation also affects a non-ethylene-dependent pathway regulating cell expansion. The phenotype of ran1-3 mutants is similar to loss-of-function ethylene receptor mutants, suggesting that RAN1 may be required to form functional ethylene receptors. Furthermore, these results suggest that copper is required not only for ethylene binding but also for the signaling function of the ethylene receptors.

  17. Colloidal and electrochemical aspects of copper-CMP

    NASA Astrophysics Data System (ADS)

    Sun, Yuxia

    Copper based interconnects with low dielectric constant layers are currently used to increase interconnect densities and reduce interconnect time delays in integrated circuits. The technology used to develop copper interconnects involves Chemical Mechanical Planarization (CMP) of copper films deposited on low-k layers (silica or silica based films), which is carried out using slurries containing abrasive particles. One issue using such a structure is copper contamination over dielectric layers (SiO2 film), if not reduced, this contamination will cause current leakage. In this study, the conditions conducive to copper contamination onto SiO2 films during Cu-CMP process were studied, and a post-CMP cleaning technique was discussed based on experimental results. It was found that the adsorption of copper onto a silica surface is kinetically fast (<0.5 minute). The amount of copper absorbed is pH and concentration dependent and affected by presence of H2O2, complexing agents, and copper corrosion inhibitor Benzotrazole. Based on de-sorption results, DI water alone was unable to reduce adsorbed copper to an acceptable level, especially for adsorption that takes place at a higher pH condition. The addition of complex agent, citric acid, proved effective in suppressing copper adsorption onto oxide silica during polishing or post-CMP cleaning by forming stable copper-CA complexes. Surface Complexation Modeling was used to simulate copper adsorption isotherms and predict the copper contamination levels on SiO2 surfaces. Another issue with the application of copper CMP is its environmental impact. CMP is a costly process due to its huge consumption of pure water and slurry. Additionally, Cu-CMP processing generates a waste stream containing certain amounts of copper and abrasive slurry particles. In this study, the separation technique electrocoagulation was investigated to remove both copper and abrasive slurry particles simultaneously. For effluent containing ˜40 ppm dissolved copper, it was found that ˜90% dissolved copper was removed from the waste streams through electroplating and in-situ chemical precipitation. The amount of copper removed through plating is impacted by membrane surface charge, type/amount of complexing agents, and solid content in the slurry suspension. The slurry particles can be removed ˜90% within 2 hours of EC through multiple mechanisms.

  18. [Effect of different soil types on the remediation of copper-pyrene compound contaminated soils by EK-oxidation process].

    PubMed

    Fan, Guang-Ping; Cang, Long; Zhou, Dong-Mei; Zhou, Li-Xiang

    2011-11-01

    The effect of different soil types (red soil,yellow-brown soil and black soil) on the electrokinetic (EK)-oxidation remediation of heavy metals-organic pollutant contaminated soil was studied in laboratory-scale experiments. Copper and pyrene were chosen as model pollutant, and 12% H2O2, 10% hydroxypropyl-beta-cyclodextrin and 0.01 mol x L(-1) NaNO3 solution were added into the anode and cathode cell. The applied voltage was 1 V x cm(-1). After 15 days of EK remediation, the removal rate of pyrene and copper in red soil, yellow-brown soil and black soil were 38.5%, 46.8%, 51.3% for pyrene and 85.0%, 22.6%, 24.1% for Cu, respectively. The high pH of black soil produced high electroosmotic flow and increased the exposure of oxidants and pollutants, meanwhile the low clay content was also conducive to the desorption of pyrene. The low pH and organic matter of red soil affected the chemical species distribution of Cu and increased its removal rate. It is concluded that soil pH, clay content and heavy metal speciation in soil are the dominant factors affecting the migration and removal efficiency of pollutants.

  19. 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

  20. Analysis of ambient pH stress response mediated by iron and copper intake in Schizosaccharomyces pombe.

    PubMed

    Higuchi, Yujiro; Mori, Hikari; Kubota, Takeo; Takegawa, Kaoru

    2018-01-01

    The molecular mechanism of tolerance to alkaline pH is well studied in model fungi Aspergillus nidulans and Saccharomyces cerevisiae. However, how fission yeast Schizosaccharomyces pombe survives under alkaline stress remains largely unknown, as the genes involved in the alkaline stress response pathways of A. nidulans and S. cerevisiae were not found in the genome of this organism. Since uptake of iron and copper into cells is important for alkaline tolerance in S. cerevisiae, here we examined whether iron and copper uptake processes were involved in conferring tolerance to alkaline stress in S. pombe. We first revealed that S. pombe wild-type strain could not grow at a pH higher than 6.7. We further found that the growths of mutants harboring disruption in the iron uptake-related gene frp1 + , fio1 + or fip1 + were severely inhibited under ambient pH stress condition. In contrast, derepression of these genes, by deletion of their repressor gene fep1 + , caused cells to acquire resistance to pH stress. Together, these results suggested that uptake of iron is essential for ambient pH tolerance in S. pombe. We also found that copper is required for the pH stress response because disruptants of ctr4 + , ctr5 + , ccc2 + and cuf1 + genes, all of which are needed for regulating intracellular Cu + , displayed ambient pH sensitivity. Furthermore, supplementing Fe 2+ and Cu 2+ ions to the culture media improved growth under ambient pH stress. Taken together, our results suggested that uptake of iron and copper is the crucial factor needed for the adaptation of S. pombe to ambient pH stress. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  1. Spectroscopic Characterization of a Green Copper Site in a Single-Domain Cupredoxin

    PubMed Central

    Roger, Magali; Biaso, Frédéric; Castelle, Cindy J.; Bauzan, Marielle; Chaspoul, Florence; Lojou, Elisabeth; Sciara, Giuliano; Caffarri, Stefano; Giudici-Orticoni, Marie-Thérèse; Ilbert, Marianne

    2014-01-01

    Cupredoxins are widespread copper-binding proteins, mainly involved in electron transfer pathways. They display a typical rigid greek key motif consisting of an eight stranded β-sandwich. A fascinating feature of cupredoxins is the natural diversity of their copper center geometry. These geometry variations give rise to drastic changes in their color, such as blue, green, red or purple. Based on several spectroscopic and structural analyses, a connection between the geometry of their copper-binding site and their color has been proposed. However, little is known about the relationship between such diversity of copper center geometry in cupredoxins and possible implications for function. This has been difficult to assess, as only a few naturally occurring green and red copper sites have been described so far. We report herein the spectrocopic characterization of a novel kind of single domain cupredoxin of green color, involved in a respiratory pathway of the acidophilic organism Acidithiobacillus ferrooxidans. Biochemical and spectroscopic characterization coupled to bioinformatics analysis reveal the existence of some unusual features for this novel member of the green cupredoxin sub-family. This protein has the highest redox potential reported to date for a green-type cupredoxin. It has a constrained green copper site insensitive to pH or temperature variations. It is a green-type cupredoxin found for the first time in a respiratory pathway. These unique properties might be explained by a region of unknown function never found in other cupredoxins, and by an unusual length of the loop between the second and the fourth copper ligands. These discoveries will impact our knowledge on non-engineered green copper sites, whose involvement in respiratory chains seems more widespread than initially thought. PMID:24932914

  2. Spectroscopic characterization of a green copper site in a single-domain cupredoxin.

    PubMed

    Roger, Magali; Biaso, Frédéric; Castelle, Cindy J; Bauzan, Marielle; Chaspoul, Florence; Lojou, Elisabeth; Sciara, Giuliano; Caffarri, Stefano; Giudici-Orticoni, Marie-Thérèse; Ilbert, Marianne

    2014-01-01

    Cupredoxins are widespread copper-binding proteins, mainly involved in electron transfer pathways. They display a typical rigid greek key motif consisting of an eight stranded β-sandwich. A fascinating feature of cupredoxins is the natural diversity of their copper center geometry. These geometry variations give rise to drastic changes in their color, such as blue, green, red or purple. Based on several spectroscopic and structural analyses, a connection between the geometry of their copper-binding site and their color has been proposed. However, little is known about the relationship between such diversity of copper center geometry in cupredoxins and possible implications for function. This has been difficult to assess, as only a few naturally occurring green and red copper sites have been described so far. We report herein the spectrocopic characterization of a novel kind of single domain cupredoxin of green color, involved in a respiratory pathway of the acidophilic organism Acidithiobacillus ferrooxidans. Biochemical and spectroscopic characterization coupled to bioinformatics analysis reveal the existence of some unusual features for this novel member of the green cupredoxin sub-family. This protein has the highest redox potential reported to date for a green-type cupredoxin. It has a constrained green copper site insensitive to pH or temperature variations. It is a green-type cupredoxin found for the first time in a respiratory pathway. These unique properties might be explained by a region of unknown function never found in other cupredoxins, and by an unusual length of the loop between the second and the fourth copper ligands. These discoveries will impact our knowledge on non-engineered green copper sites, whose involvement in respiratory chains seems more widespread than initially thought.

  3. 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

  4. Ablative and transport fractionation of trace elements during laser sampling of glass and copper

    NASA Astrophysics Data System (ADS)

    Outridge, P. M.; Doherty, W.; Gregoire, D. C.

    1997-12-01

    The fractionation of trace elements due to ablation and transport processes was quantified during Q-switched infrared laser sampling of glass and copper reference materials. Filter-trapping of the ablated product at different points in the sample introduction system showed ablation and transport sometimes caused opposing fractionation effects, leading to a confounded measure of overall (ablative + transport) fractionation. An unexpected result was the greater ablative fractionation of some elements (Au, Ag, Bi, Te in glass and Au, Be, Bi, Ni, Te in copper) at a higher laser fluence of 1.35 × 10 4W cm -2 than at 0.62 × 10 4W cm -2, which contradicted predictions from modelling studies of ablation processes. With glass, there was an inverse logarithmic relationship between the extent of ablative and overall fractionation and element oxide melting point (OMPs), with elements with OMPs < 1000° C exhibiting overall concentration increases of 20-1340%. Fractionation during transport was quantitatively important for most certified elements in copper, and for the most volatile elements (Au, Ag, Bi, Te) in glass. Elements common to both matrices showed 50-100% higher ablative fractionation in copper, possibly because of greater heat conductance away from the ablation site causing increased element volatilisation or zone refinement. These differences between matrices indicate that non-matrix-matched standardisation is likely to provide inaccurate calibration of laser ablation inductively coupled plasma-mass spectrometry analyses of at least some elements.

  5. Variation of calcium, copper and iron levels in serum, bile and stone samples of patients having different types of gallstone: A comparative study.

    PubMed

    Khan, Mustafa; Kazi, Tasneem Gul; Afridi, Hassan Imran; Sirajuddin; Bilal, Muhammad; Akhtar, Asma; Khan, Sabir; Kadar, Salma

    2017-08-01

    Epidemiological data among the human population has shown a significantly increased incidence of gallstone (GS) disease worldwide. It was studied that some essential (calcium) and transition elements (iron and copper) in bile play an important role in the development of GS. The estimation of calcium, copper and iron were carried out in the serum, gall bladder bile and different types of GS (cholesterol, mixed and pigmented) of 172 patients, age ranged 20-55years. For comparative purpose age matched referents not suffering from GS diseases were also selected. Biliary concentrations of calcium (Ca), iron (Fe) and copper (Cu) were correlated with their concentrations in serum and different types of GS samples. The ratio of Ca, Fe and Cu in bile with serum was also calculated. Understudy metals were determined by flame atomic absorption spectroscopy after acid decomposition of matrices of selected samples. The Ca concentrations in serum samples were significantly higher in patients with pigmented GS as compared to controls (p<0.005), whereas for patients having cholesterol and mixed GS the concentrations were on the lower side. Biliary Ca concentrations of patients were found to be higher than controls, but difference was significant for pigmented GS patients (p>0.001). The contents of Cu and Fe in serum and bile of all patients (except female cholesterol GS patient have low serum iron concentration) were found to be higher than control, but difference was significant in those patients who have pigmented GS. The concentration of Ca, Fe and Cu in different types GS were found in the order, Pigmented>mixed>cholesterol. The bile/serum ratio for Ca, Cu and Fe was found to be significantly higher in pigmented GS patients. Gall bladder bile was slightly alkaline in patients as compared to referents. The density of bile was found to be higher in patients as compared to the referents. Various functional groups present in different types of GS samples were confirmed by Fourier transform infra-red spectroscopy. The higher density and pH of bile, elevated concentrations of transition elements in all types of biological samples (serum, bile and GS), could be an important factor for the formation of different types of GS. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Coating Galvanized Steel

    DTIC Science & Technology

    1989-06-01

    bonding of topcoats to smooth galvanizing have lead to such practices as washing with vinegar , washing with copper sulfate solution, or weathering before...of special treatments other than weathering: "The "home cure" type of treatments such as washing the surface with vinegar , acetic acid, cider, copper... alcohol . The wash primer used was MIL-P-15328 (Formula 117). It is spray- applied to give 0.3- to 0.5-mil dry film thickness and is used on ships to

  7. Ambipolar carrier transport properties and molecular packing structure of octahexyl-substituted copper phthalocyanine

    NASA Astrophysics Data System (ADS)

    Watanabe, Ken; Watanabe, Koichi; Tohnai, Norimitsu; Itani, Hiromichi; Shimizu, Yo; Fujii, Akihiko; Ozaki, Masanori

    2018-04-01

    The charge carrier mobility of a solution-processable low-molecular-weight organic semiconductor material, i.e., 1,4,8,11,15,18,22,25-octahexylphthalocyanine copper complex (C6PcCu), was investigated by the time-of-flight technique. The anomalous ambipolar carrier mobility was discussed from the viewpoint of the molecular packing structure, which was clarified by single-crystal X-ray structure analysis. In the comparison between the molecular packing structures of C6PcCu and its metal-free-type homologue, it was found that the difference in carrier mobility originates from the rotation of the molecule, which is caused by the steric hindrance due to the introduction of a center metal and the interpenetration of the nonperipheral alkyl chains.

  8. Urinary Copper Elevation in a Mouse Model of Wilson's Disease Is a Regulated Process to Specifically Decrease the Hepatic Copper Load

    PubMed Central

    Gray, Lawrence W.; Peng, Fangyu; Molloy, Shannon A.; Pendyala, Venkata S.; Muchenditsi, Abigael; Muzik, Otto; Lee, Jaekwon; Kaplan, Jack H.; Lutsenko, Svetlana

    2012-01-01

    Body copper homeostasis is regulated by the liver, which removes excess copper via bile. In Wilson's disease (WD), this function is disrupted due to inactivation of the copper transporter ATP7B resulting in hepatic copper overload. High urinary copper is a diagnostic feature of WD linked to liver malfunction; the mechanism behind urinary copper elevation is not fully understood. Using Positron Emission Tomography-Computed Tomography (PET-CT) imaging of live Atp7b−/− mice at different stages of disease, a longitudinal metal analysis, and characterization of copper-binding molecules, we show that urinary copper elevation is a specific regulatory process mediated by distinct molecules. PET-CT and atomic absorption spectroscopy directly demonstrate an age-dependent decrease in the capacity of Atp7b−/− livers to accumulate copper, concomitant with an increase in urinary copper. This reciprocal relationship is specific for copper, indicating that cell necrosis is not the primary cause for the initial phase of metal elevation in the urine. Instead, the urinary copper increase is associated with the down-regulation of the copper-transporter Ctr1 in the liver and appearance of a 2 kDa Small Copper Carrier, SCC, in the urine. SCC is also elevated in the urine of the liver-specific Ctr1 −/− knockouts, which have normal ATP7B function, suggesting that SCC is a normal metabolite carrying copper in the serum. In agreement with this hypothesis, partially purified SCC-Cu competes with free copper for uptake by Ctr1. Thus, hepatic down-regulation of Ctr1 allows switching to an SCC-mediated removal of copper via kidney when liver function is impaired. These results demonstrate that the body regulates copper export through more than one mechanism; better understanding of urinary copper excretion may contribute to an improved diagnosis and monitoring of WD. PMID:22802922

  9. Systems and methods for solar cells with CIS and CIGS films made by reacting evaporated copper chlorides with selenium

    DOEpatents

    Albin, David S.; Noufi, Rommel

    2015-06-09

    Systems and methods for solar cells with CIS and CIGS films made by reacting evaporated copper chlorides with selenium are provided. In one embodiment, a method for fabricating a thin film device comprises: providing a semiconductor film comprising indium (In) and selenium (Se) upon a substrate; heating the substrate and the semiconductor film to a desired temperature; and performing a mass transport through vapor transport of a copper chloride vapor and se vapor to the semiconductor film within a reaction chamber.

  10. Effects of copper source and concentration on in vitro phytate phosphorus hydrolysis by phytase.

    PubMed

    Pang, Yanfang; Applegate, Todd J

    2006-03-08

    Five copper (Cu) sources were studied at pH 2.5, 5.5, and 6.5 to determine how Cu affects phytate phosphorus (PP) hydrolysis by phytase at concentrations up to 500 mg/kg diet (60 min, 40-41 degrees C). Subsequently, Cu solubility with and without sodium phytate was measured. Adding Cu inhibited PP hydrolysis at pH 5.5 and pH 6.5 (P < 0.05). This inhibition was greater with higher concentrations of Cu. Tri-basic copper chloride and copper lysinate inhibited PP hydrolysis much less than copper sulfate pentahydrate, copper chloride, and copper citrate (P < 0.05). A strong negative relationship was observed between PP hydrolysis and soluble Cu at pH 5.5 (r = -0.76, P < 0.0001) and 6.5 (r = -0.54, P < 0.0001). In conclusion, pH, Cu concentration, and source influenced PP hydrolysis by phytase in vitro and were related to the amount of soluble Cu and the formation of insoluble copper-phytin complexes.

  11. Copper tolerance in Frankia sp. strain EuI1c involves surface binding and copper transport.

    PubMed

    Rehan, Medhat; Furnholm, Teal; Finethy, Ryan H; Chu, Feixia; El-Fadly, Gomaah; Tisa, Louis S

    2014-09-01

    Several Frankia strains have been shown to be copper-tolerant. The mechanism of their copper tolerance was investigated for Frankia sp. strain EuI1c. Copper binding was shown by binding studies. Unusual globular structures were observed on the surface of the bacterium. These globular structures were composed of aggregates containing many relatively smaller "leaf-like" structures. Scanning electron microscopy with energy-dispersive X-ray (SEM-EDAX) analysis of these structures indicated elevated copper and phosphate levels compared to the control cells. Fourier transform infrared spectroscopy (FTIR) analysis indicated an increase in extracellular phosphate on the cell surface of copper-stressed cells. Bioinformatics' analysis of the Frankia sp. strain EuI1c genome revealed five potential cop genes: copA, copZ, copC, copCD, and copD. Experiments with Frankia sp. strain EuI1c using qRT-PCR indicated an increase in messenger RNA (mRNA) levels of the five cop genes upon Cu(2+) stress. After 5 days of Cu(2+) stress, the copA, copZ, copC, copCD, and copD mRNA levels increased 25-, 8-, 18-, 18-, and 25-fold, respectively. The protein profile of Cu(2+)-stressed Frankia sp. strain EuI1c cells revealed the upregulation of a 36.7 kDa protein that was identified as FraEuI1c_1092 (sulfate-binding periplasmic transport protein). Homologues of this gene were only present in the genomes of the Cu(2+)-resistant Frankia strains (EuI1c, DC12, and CN3). These data indicate that copper tolerance by Frankia sp. strain EuI1c involved the binding of copper to the cell surface and transport proteins.

  12. Exploratory Disposal and Reuse Feasibility Analysis of Winter Maintenance Wash Water.

    PubMed

    Ullinger, Heather L; Kennedy, Marla J; Schneider, William H; Miller, Christopher M

    2016-01-01

    The Ohio Department of Transportation has more than 60 facilities without sewer access generating approximately 19 million gallons of winter maintenance wash water. Off-site disposal is costly, creating the need for sustainable management strategies. The objective of this study was to conduct an exploratory feasibility analysis to assess wash water disposal and potential reuse as brine. Based on a comprehensive literature review and relevant environmental chemistry, a sampling protocol consisting of 31 water quality constituents was utilized for monthly sampling at three geographically distinct Ohio Department of Transportation garages during the winter of 2012. Results were compared to local disposal and reuse guidance limits. Three constituents, including a maximum copper concentration of 858 ppb, exceeded disposal limits, and many constituents also failed to meet reuse limits. Some concentrations were orders of magnitude higher than reuse limits and suggest pre-treatment would be necessary if wash water were reused as brine. These water quality results, in conjunction with copper chemical equilibrium modeling, show pH and dissolved carbon both significantly impact the total dissolved copper concentration and should be measured to assess reuse potential. The sampling protocol and specific obstacles highlighted in this paper aid in the future development of sustainable wash water management strategies.

  13. Exploratory Disposal and Reuse Feasibility Analysis of Winter Maintenance Wash Water

    PubMed Central

    2016-01-01

    The Ohio Department of Transportation has more than 60 facilities without sewer access generating approximately 19 million gallons of winter maintenance wash water. Off-site disposal is costly, creating the need for sustainable management strategies. The objective of this study was to conduct an exploratory feasibility analysis to assess wash water disposal and potential reuse as brine. Based on a comprehensive literature review and relevant environmental chemistry, a sampling protocol consisting of 31 water quality constituents was utilized for monthly sampling at three geographically distinct Ohio Department of Transportation garages during the winter of 2012. Results were compared to local disposal and reuse guidance limits. Three constituents, including a maximum copper concentration of 858 ppb, exceeded disposal limits, and many constituents also failed to meet reuse limits. Some concentrations were orders of magnitude higher than reuse limits and suggest pre-treatment would be necessary if wash water were reused as brine. These water quality results, in conjunction with copper chemical equilibrium modeling, show pH and dissolved carbon both significantly impact the total dissolved copper concentration and should be measured to assess reuse potential. The sampling protocol and specific obstacles highlighted in this paper aid in the future development of sustainable wash water management strategies. PMID:26908148

  14. 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.

  15. Understanding Copper Isotope Behavior in the High Temperature Magmatic-Hydrothermal Porphyry Environment

    NASA Astrophysics Data System (ADS)

    Gregory, Melissa J.; Mathur, Ryan

    2017-11-01

    Copper stable isotope geochemistry has the potential to constrain aspects of ore deposit formation once variations in the isotopic data can be related to the physiochemical conditions during metal deposition. This study presents Cu isotope ratios for samples from the Pebble porphyry Cu-Au-Mo deposit in Alaska. The δ65Cu values for hypogene copper sulfides range from -2.09‰ to 1.11‰ and show linear correlations with the δ18O isotope ratios calculated for the fluid in equilibrium with the hydrothermal alteration minerals in each sample. Samples with sodic-potassic, potassic, and illite alteration display a negative linear correlation between the Cu and O isotope results. This suggests that fractionation of Cu isotopes between the fluid and precipitating chalcopyrite is positive as the hydrothermal fluid is evolving from magmatic to mixed magmatic-meteoric compositions. Samples with advanced argillic alteration display a weak positive linear correlation between Cu and O isotope results consistent with small negative fluid-chalcopyrite Cu isotope fractionation during fluid evolution. The hydrothermal fluids that formed sodic-potassic, potassic, and illite alteration likely transported Cu as CuHS0. Hydrothermal fluids that resulted in advanced argillic alteration likely transport Cu as CuCl2-. The pH conditions also control Cu isotope fractionation, consistent with previous experimental work. Larger fractionation factors were found between fluids and chalcopyrite precipitating under neutral conditions contrasting with small fractionation factors calculated between fluids and chalcopyrite precipitating under acidic conditions. Therefore, this study proposes that hydrothermal fluid compositions and pH conditions are related to Cu isotope variations in high temperature magmatic-hydrothermal deposits.

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

    PubMed

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

    2014-05-15

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

  17. 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.

  18. 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

  19. Exogenous addition of histidine reduces copper availability in the yeast Saccharomyces cerevisiae.

    PubMed

    Watanabe, Daisuke; Kikushima, Rie; Aitoku, Miho; Nishimura, Akira; Ohtsu, Iwao; Nasuno, Ryo; Takagi, Hiroshi

    2014-07-07

    The basic amino acid histidine inhibited yeast cell growth more severely than lysine and arginine. Overexpression of CTR1 , which encodes a high-affinity copper transporter on the plasma membrane, or addition of copper to the medium alleviated this cytotoxicity. However, the intracellular level of copper ions was not decreased in the presence of excess histidine. These results indicate that histidine cytotoxicity is associated with low copper availability inside cells, not with impaired copper uptake. Furthermore, histidine did not affect cell growth under limited respiration conditions, suggesting that histidine cytotoxicity is involved in deficiency of mitochondrial copper.

  20. Excretion of laccase by sycamore (Acer pseudoplatanus L.) cells. Purification and properties of the enzyme.

    PubMed Central

    Bligny, R; Douce, R

    1983-01-01

    A laccase-type polyphenol oxidase is excreted by sycamore cells (Acer pseudoplatanus L.) cells. The enzyme has been purified by classical purification techniques. It is a blue copper protein of Mr 97 000, containing 45% carbohydrate and 0.24% copper. This protein consists of one single unit and the copper content corresponds to four copper atoms per protein molecule. The specific activity of the purified extracellular sycamore-cell laccase measured at pH 6.6 (optimum pH) and in the presence of 20mM-4-methhylcatechol (optimum substrate conditions) corresponded to an oxygen uptake of 32 000 nmol of O2/min per mg of protein. Under these conditions, the catalytic-centre activity of the enzyme reached 100 s-1. The excretion of laccase by sycamore cells is significant, being about 2% of the total protein synthesized by the cells during the exponential phase of growth, and is independent of cell growth. The physiological significance and the problems raised by the passage of this protein across the cytoplasmic membrane are discussed. PMID:6847630

  1. Effect of in ovo supplementation of nano forms of zinc, copper, and selenium on post-hatch performance of broiler chicken.

    PubMed

    Joshua, P Patric; Valli, C; Balakrishnan, V

    2016-03-01

    Nanoparticles can bypass conventional physiological ways of nutrient distribution and transport across tissue and cell membranes, as well as protect compounds against destruction prior to reaching their targets. In ovo administration of nanoparticles, may be seen as a new method of nano-nutrition, providing embryos with an additional quantity of nutrients. The aim of the study is to examine the effect of in ovo supplementation of nano forms of zinc, copper and selenium on the hatchability and post hatch performance of broiler chicken. Nano form of zinc at 20, 40, 60 and 80 µg/egg, nano form of copper at 4, 8, 12 and 16 µg/egg and nano form of selenium at 0.075, 0.15, 0.225 and 0.3 µg/egg were in ovo supplemented (18(th) day incubation, amniotic route) in fertile broiler eggs. Control group in ovo fed with normal saline alone was also maintained. Each treatment had thirty replicates. Parameters such as hatchability, hatch weight and post hatch performance were studied. In ovo feeding of nano minerals were not harmful to the developing embryo and did not influence the hatchability. Significantly (p<0.05) best feed efficiency for nano forms of zinc (2.16), copper (2.46) and selenium (2.51) were observed, when 40, 4 and 0.225 µg/egg respectively were in ovo supplemented. Except in nano form of copper at 12 µg per egg which had significantly (p<0.05) highest breast muscle percentage there was no distinct trend to indicate that dressing percentage or breast muscle yield was influenced in other treatments. Nano forms of zinc, copper and selenium can be prepared at laboratory conditions. In ovo feeding of nano forms of zinc, copper and selenium at 18(th) day of incubation through amniotic route does not harm the developing embryo, does not affect hatchability.

  2. Effect of in ovo supplementation of nano forms of zinc, copper, and selenium on post-hatch performance of broiler chicken

    PubMed Central

    Joshua, P. Patric; Valli, C.; Balakrishnan, V.

    2016-01-01

    Background and Aim: Nanoparticles can bypass conventional physiological ways of nutrient distribution and transport across tissue and cell membranes, as well as protect compounds against destruction prior to reaching their targets. In ovo administration of nanoparticles, may be seen as a new method of nano-nutrition, providing embryos with an additional quantity of nutrients. The aim of the study is to examine the effect of in ovo supplementation of nano forms of zinc, copper and selenium on the hatchability and post hatch performance of broiler chicken. Materials and Methods: Nano form of zinc at 20, 40, 60 and 80 µg/egg, nano form of copper at 4, 8, 12 and 16 µg/egg and nano form of selenium at 0.075, 0.15, 0.225 and 0.3 µg/egg were in ovo supplemented (18th day incubation, amniotic route) in fertile broiler eggs. Control group in ovo fed with normal saline alone was also maintained. Each treatment had thirty replicates. Parameters such as hatchability, hatch weight and post hatch performance were studied. Results: In ovo feeding of nano minerals were not harmful to the developing embryo and did not influence the hatchability. Significantly (p<0.05) best feed efficiency for nano forms of zinc (2.16), copper (2.46) and selenium (2.51) were observed, when 40, 4 and 0.225 µg/egg respectively were in ovo supplemented. Except in nano form of copper at 12 µg per egg which had significantly (p<0.05) highest breast muscle percentage there was no distinct trend to indicate that dressing percentage or breast muscle yield was influenced in other treatments. Conclusion: Nano forms of zinc, copper and selenium can be prepared at laboratory conditions. In ovo feeding of nano forms of zinc, copper and selenium at 18th day of incubation through amniotic route does not harm the developing embryo, does not affect hatchability. PMID:27057113

  3. Dextran-Catechin: An anticancer chemically-modified natural compound targeting copper that attenuates neuroblastoma growth

    PubMed Central

    Vittorio, Orazio; Brandl, Miriam; Cirillo, Giuseppe; Kimpton, Kathleen; Hinde, Elizabeth; Gaus, Katharina; Yee, Eugene; Kumar, Naresh; Duong, Hien; Fleming, Claudia; Haber, Michelle; Norris, Murray; Boyer, Cyrille; Kavallaris, Maria

    2016-01-01

    Neuroblastoma is frequently diagnosed at advanced stage disease and treatment includes high dose chemotherapy and surgery. Despite the use of aggressive therapy survival rates are poor and children that survive their disease experience long term side effects from their treatment, highlighting the need for effective and less toxic therapies. Catechin is a natural polyphenol with anti-cancer properties and limited side effects, however its mechanism of action is unknown. Here we report that Dextran-Catechin, a conjugated form of catechin that increases serum stability, is preferentially and markedly active against neuroblastoma cells having high levels of intracellular copper, without affecting non-malignant cells. Copper transporter 1 (CTR1) is the main transporter of copper in mammalian cells and it is upregulated in neuroblastoma. Functional studies showed that depletion of CTR1 expression reduced intracellular copper levels and led to a decrease in neuroblastoma cell sensitivity to Dextran-Catechin, implicating copper in the activity of this compound. Mechanistically, Dextran-Catechin was found to react with copper, inducing oxidative stress and decreasing glutathione levels, an intracellular antioxidant and regulator of copper homeostasis. In vivo, Dextran-Catechin significantly attenuated tumour growth in human xenograft and syngeneic models of neuroblastoma. Thus, Dextran-Catechin targets copper, inhibits tumour growth, and may be valuable in the treatment of aggressive neuroblastoma and other cancers dependent on copper for their growth. PMID:27374085

  4. Emergency contraception with a copper IUD or oral levonorgestrel: an observational study of 1-year pregnancy rates.

    PubMed

    Turok, David K; Jacobson, Janet C; Dermish, Amna I; Simonsen, Sara E; Gurtcheff, Shawn; McFadden, Molly; Murphy, Patricia A

    2014-03-01

    We investigated the 1-year pregnancy rates for emergency contraception (EC) users who selected the copper T380 intrauterine device (IUD) or oral levonorgestrel (LNG) for EC. This prospective study followed women for 1 year after choosing either the copper T380 IUD or oral LNG for EC. The study was powered to detect a 6% difference in pregnancy rates within the year after presenting for EC. Of the 542 women who presented for EC, agreed to participate in the trial and met the inclusion criteria, 215 (40%) chose the copper IUD and 327 (60%) chose oral LNG. In the IUD group, 127 (59%) were nulligravid. IUD insertion failed in 42 women (19%). The 1-year follow-up rate was 443/542 (82%); 64% of IUD users contacted at 1 year still had their IUDs in place. The 1-year cumulative pregnancy rate in women choosing the IUD was 6.5% vs. 12.2% in those choosing oral LNG [hazard ratio (HR) 0.53, 95% confidence interval (CI): 0.29-0.97, p=.041]. By type of EC method actually received, corresponding values were 5.2% for copper IUD users vs. 12.3% for oral LNG users (HR 0.42, 95% CI: 0.20-0.85, p=.017). A multivariable logistic regression model controlling for demographic variables demonstrates that women who chose the IUD for EC had fewer pregnancies in the following year than those who chose oral LNG (HR 0.50, 95% CI: 0.26-0.96, p=.037). One year after presenting for EC, women choosing the copper IUD for EC were half as likely to have a pregnancy compared to those choosing oral LNG. Compared to EC users who choose oral levonorgestrel, those who select the copper IUD have lower rates of pregnancy in the next year. Greater use of the copper IUD for EC may lower rates of unintended pregnancy in high-risk women. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. Metal ions in macrophage antimicrobial pathways: emerging roles for zinc and copper

    PubMed Central

    Stafford, Sian L.; Bokil, Nilesh J.; Achard, Maud E. S.; Kapetanovic, Ronan; Schembri, Mark A.; McEwan, Alastair G.; Sweet, Matthew J.

    2013-01-01

    The immunomodulatory and antimicrobial properties of zinc and copper have long been appreciated. In addition, these metal ions are also essential for microbial growth and survival. This presents opportunities for the host to either harness their antimicrobial properties or limit their availability as defence strategies. Recent studies have shed some light on mechanisms by which copper and zinc regulation contribute to host defence, but there remain many unanswered questions at the cellular and molecular levels. Here we review the roles of these two metal ions in providing protection against infectious diseases in vivo, and in regulating innate immune responses. In particular, we focus on studies implicating zinc and copper in macrophage antimicrobial pathways, as well as the specific host genes encoding zinc transporters (SLC30A, SLC39A family members) and CTRs (copper transporters, ATP7 family members) that may contribute to pathogen control by these cells. PMID:23738776

  6. Synthesis, structure and catechol-oxidase activity of copper(II) complexes of 17-hydroxy-16-(N-3-oxo-prop-1-enyl)amino steroids.

    PubMed

    Wegner, Rainer; Dubs, Manuela; Görls, Helmar; Robl, Christian; Schönecker, Bruno; Jäger, Ernst-G

    2002-09-01

    Copper is next to iron the most important element in the biological transport, storage and in redox reactions of dioxygen. A bioanalogous activation of dioxygen with copper complexes is used for catalytical epoxidation, allylic hydroxylation and oxidative coupling of aromatic substrates, for example. With stereochemical information in form of chiral ligands, enantioselective reactions may be possible. Another aspect of interest on copper catalyzed reactions with dioxygen is that the exact mechanism and biological function of some enzymes (especially catechol oxidase) is yet not fully clear. For studies mimicking the copper-containing catechol oxidase appropriate chiral steroid ligands with defined stereochemistry and conformation have been synthesized. The four diastereomeric 16,17-aminoalcohols of the 3-methoxy-estra-1,3,5(10)-triene series have been condensed with salicylic aldehyde and different beta-ketoenols to the chiral ligand types 1-5. These compounds with different steric and electronic properties and different arrangements of the neighboring hydroxy and nitrogen functions were reacted with copper(II) acetate to copper complexes. The structure of these complexes will be discussed. The bioanalogous oxidation of 3,5-di-tbutyl-catechol (dtbc) to the corresponding quinone was catalyzed by most of the complexes, indicating their ability to activate dioxygen. The trans configurations c and d showed an activity one magnitude higher than the cis configurations a and b. Comparing compounds with the same diastereomeric configuration, the main influence was that of the peripheral R(1-3) substituents at the beta-ketoenaminic group which are useful for the fine-tuning of the properties of the copper atoms like redox potential and Lewis acidity.

  7. 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.

  8. 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.

  9. Face-on stacking and enhanced out-of-plane hole mobility in graphene-templated copper phthalocyanine.

    PubMed

    Mativetsky, Jeffrey M; Wang, He; Lee, Stephanie S; Whittaker-Brooks, Luisa; Loo, Yueh-Lin

    2014-05-25

    Efficient out-of-plane charge transport is required in vertical device architectures, such as organic solar cells and organic light emitting diodes. Here, we show that graphene, transferred onto different technologically-relevant substrates, can be used to induce face-on molecular stacking and improve out-of-plane hole transport in copper phthalocyanine thin films.

  10. Understanding and control of bipolar self-doping in copper nitride

    NASA Astrophysics Data System (ADS)

    Fioretti, Angela N.; Schwartz, Craig P.; Vinson, John; Nordlund, Dennis; Prendergast, David; Tamboli, Adele C.; Caskey, Christopher M.; Tuomisto, Filip; Linez, Florence; Christensen, Steven T.; Toberer, Eric S.; Lany, Stephan; Zakutayev, Andriy

    2016-05-01

    Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu3N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu3N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu3N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu3N with 1017 electrons/cm3 for low growth temperature (≈35 °C) and p-type with 1015 holes/cm3-1016 holes/cm3 for elevated growth temperatures (50 °C-120 °C). Mobility for both types of Cu3N was ≈0.1 cm2/Vs-1 cm2/Vs. Additionally, temperature-dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that VCu defects form preferentially in p-type Cu3N, while Cui defects form preferentially in n-type Cu3N, suggesting that Cu3N is a compensated semiconductor with conductivity type resulting from a balance between donor and acceptor defects. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu3N that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials and provide a framework that can be applied when considering the properties of such materials in general.

  11. Copper accumulation in senescent cells: Interplay between copper transporters and impaired autophagy.

    PubMed

    Masaldan, Shashank; Clatworthy, Sharnel A S; Gamell, Cristina; Smith, Zoe M; Francis, Paul S; Denoyer, Delphine; Meggyesy, Peter M; Fontaine, Sharon La; Cater, Michael A

    2018-06-01

    Cellular senescence is characterized by irreversible growth arrest incurred through either replicative exhaustion or by pro-oncogenic cellular stressors (radioactivity, oxidative stress, oncogenic activation). The enrichment of senescent cells in tissues with age has been associated with tissue dyshomeostasis and age-related pathologies including cancers, neurodegenerative disorders (e.g. Alzheimer's, Parkinson's, etc.) and metabolic disorders (e.g. diabetes). We identified copper accumulation as being a universal feature of senescent cells [mouse embryonic fibroblasts (MEF), human prostate epithelial cells and human diploid fibroblasts] in vitro. Elevated copper in senescent MEFs was accompanied by elevated levels of high-affinity copper uptake protein 1 (Ctr1), diminished levels of copper-transporting ATPase 1 (Atp7a) (copper export) and enhanced antioxidant defence reflected by elevated levels of glutathione (GSH), superoxide dismutase 1 (SOD1) and glutaredoxin 1 (Grx1). The levels of intracellular copper were further increased in senescent MEFs cultured in copper supplemented medium and in senescent Mottled Brindled (Mo br ) MEFs lacking functional Atp7a. Finally, we demonstrated that the restoration/preservation of autophagic-lysosomal degradation in senescent MEFs following rapamycin treatment correlated with attenuation of copper accumulation in these cells despite a further decrease in Atp7a levels. This study for the first time establishes a link between Atp7a and the autophagic-lysosomal pathway, and a requirement for both to effect efficient copper export. Such a connection between cellular autophagy and copper homeostasis is significant, as both have emerged as important facets of age-associated degenerative disease. Copyright © 2018. Published by Elsevier B.V.

  12. Does Dietary Copper Supplementation enhance or diminish PCB126 Toxicity in Rodent Liver?

    PubMed Central

    Lai, Ian K.; Klaren, William D.; Li, Miao; Wels, Brian; Simmons, Donald L.; Olivier, Alicia K.; Haschek, Wanda M.; Wang, Kai; Ludewig, Gabriele; Robertson, Larry W.

    2013-01-01

    Copper is essential for the function of the mitochondrial electron transport chain and several antioxidant proteins. However, in its free form copper can participate in Fenton-like reactions that produce reactive hydroxyl radicals. Aryl-hydrocarbon receptor (AhR) agonists, including the most potent polychlorinated biphenyl (PCB) congener, 3,3',4,4',5-pentachlorobiphenyl (PCB126), increase copper levels in rodent livers. This is accompanied by biochemical and toxic changes. To assess the involvement of copper in PCB toxicity, male Sprague Dawley rats were fed an AIN-93G diet with differing dietary copper levels: low (2 ppm), adequate (6 ppm), and high (10 ppm). After three weeks, rats from each group were given a single ip injection of corn oil (control), 1, or 5 μmol/kg body weight PCB126. Two weeks following injections, biochemical and morphological markers of hepatic toxicity, trace metal status, and hepatic gene expression of metalloproteins were evaluated. Increasing dietary copper was associated with elevated tissue levels of copper and ceruloplasmin. In the livers of PCB126-treated rats the hallmark signs of AhR activation were present, including increased cytochrome P-450 and lipid levels, and decreased glutathione. In addition a doubling of hepatic copper levels was seen and overall metals homeostasis was disturbed, resulting in decreased hepatic selenium, manganese, zinc and iron. Expression of key metalloproteins was either decreased (cytochrome c oxidase), unchanged (ceruloplasmin and CuZnSOD) or increased (tyrosinase, metallothionein 1 and 2) with exposure to PCB126. Increases in metallothionein may contribute/reflect the increased copper seen. Alterations in dietary copper did not amplify or abrogate the hepatic toxicity of PCB126. PCB126 toxicity, i.e. oxidative stress and steatosis, is clearly associated with disturbed metals homeostasis. Understanding the mechanisms of this disturbance may provide tools to prevent liver toxicity by other AhR agonists. PMID:23527585

  13. Genetic variability of psychrotolerant Acidithiobacillus ferrivorans revealed by (meta)genomic analysis.

    PubMed

    González, Carolina; Yanquepe, María; Cardenas, Juan Pablo; Valdes, Jorge; Quatrini, Raquel; Holmes, David S; Dopson, Mark

    2014-11-01

    Acidophilic microorganisms inhabit low pH environments such as acid mine drainage that is generated when sulfide minerals are exposed to air. The genome sequence of the psychrotolerant Acidithiobacillus ferrivorans SS3 was compared to a metagenome from a low temperature acidic stream dominated by an A. ferrivorans-like strain. Stretches of genomic DNA characterized by few matches to the metagenome, termed 'metagenomic islands', encoded genes associated with metal efflux and pH homeostasis. The metagenomic islands were enriched in mobile elements such as phage proteins, transposases, integrases and in one case, predicted to be flanked by truncated tRNAs. Cus gene clusters predicted to be involved in copper efflux and further Cus-like RND systems were predicted to be located in metagenomic islands and therefore, constitute part of the flexible gene complement of the species. Phylogenetic analysis of Cus clusters showed both lineage specificity within the Acidithiobacillus genus as well as niche specificity associated with an acidic environment. The metagenomic islands also contained a predicted copper efflux P-type ATPase system and a polyphosphate kinase potentially involved in polyphosphate mediated copper resistance. This study identifies genetic variability of low temperature acidophiles that likely reflects metal resistance selective pressures in the copper rich environment. Copyright © 2014 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

  14. Failure Analysis of Pitted Copper Pipes Used in Underground Water and Preventive Measures

    NASA Astrophysics Data System (ADS)

    Nam, Gi-ho; Lee, Jong-kwon; Kim, Kyung-ja

    2018-05-01

    This study performed an experiment on the causes of pitting corrosion in a copper tubing used for a sprinkler system. Corrosion products of a copper tubing that sustained pitting corrosion were collected and cultured in Culture medium [Luria-Bertani, Brain heart infusion, Tryptic soy broth (TSB), R2A]. Four types of bacteria were found through identification: Micrococcus luteus sp (species)., Staphylococcus sp., Sphingomonas sp., and Bacillus sp. The copper toxicity test was performed for each microorganism. Among the four microorganisms, Micrococcus luteus sp. showed good growth in the environment containing copper ions. On the immersion test, changes in pH and Optical density were measured; On the inductively coupled plasma optical emission spectrometry test, the copper concentration of each culture medium was measured. The surface of each copper sample was observed using a scanning electron microscope. The corrosion potential of a copper sample, after 48 h exposure of the TSB medium containing Micrococcus luteus sp., was measured using a potentiodynamic polarization experiment. The next experiment was conducted to prevent microbial corrosion by suppressing the growth of microorganisms. Six 30 ml TSB culture media with controlled pH value of 4, 5, 6, 7, 8, and 9 through HCl and NaOH were manufactured. Then the microorganisms were cultured in 37 °C 133 rpm, of which the growth status was checked every 24 h for 3 days. It was found that microorganisms did not grow on culture media with the pH value of 6 and lower. The same experiment conducted on culture media controlled with acetic acid, nitric acid, and sulfuric acid, also showed no growth of microorganisms on media with pH value of 6 and lower. Six 5 ml TSB culture media each containing 0.5, 0.25, 0.125, 0.0625, 0.0312%, and 0.0156% NaOCl and NaOBr as germicides were manufactured. 0.01 μl of microorganisms were inoculated on the media and cultured in 37 °C for 48 h. It was found that microorganisms did not grow in media with NaOCl and NaOBr concentration of 0.0625% and higher. Therefore, it can be suggested that in environments with pH value of 6 or lower, or NaOCl and NaOBr concentration of higher than 0.0625% suppresses microbial growth, thereby preventing microbial corrosion.

  15. Failure Analysis of Pitted Copper Pipes Used in Underground Water and Preventive Measures

    NASA Astrophysics Data System (ADS)

    Nam, Gi-ho; Lee, Jong-kwon; Kim, Kyung-ja

    2018-03-01

    This study performed an experiment on the causes of pitting corrosion in a copper tubing used for a sprinkler system. Corrosion products of a copper tubing that sustained pitting corrosion were collected and cultured in Culture medium [Luria-Bertani, Brain heart infusion, Tryptic soy broth (TSB), R2A]. Four types of bacteria were found through identification: Micrococcus luteus sp (species)., Staphylococcus sp., Sphingomonas sp., and Bacillus sp. The copper toxicity test was performed for each microorganism. Among the four microorganisms, Micrococcus luteus sp. showed good growth in the environment containing copper ions. On the immersion test, changes in pH and Optical density were measured; On the inductively coupled plasma optical emission spectrometry test, the copper concentration of each culture medium was measured. The surface of each copper sample was observed using a scanning electron microscope. The corrosion potential of a copper sample, after 48 h exposure of the TSB medium containing Micrococcus luteus sp., was measured using a potentiodynamic polarization experiment. The next experiment was conducted to prevent microbial corrosion by suppressing the growth of microorganisms. Six 30 ml TSB culture media with controlled pH value of 4, 5, 6, 7, 8, and 9 through HCl and NaOH were manufactured. Then the microorganisms were cultured in 37 °C 133 rpm, of which the growth status was checked every 24 h for 3 days. It was found that microorganisms did not grow on culture media with the pH value of 6 and lower. The same experiment conducted on culture media controlled with acetic acid, nitric acid, and sulfuric acid, also showed no growth of microorganisms on media with pH value of 6 and lower. Six 5 ml TSB culture media each containing 0.5, 0.25, 0.125, 0.0625, 0.0312%, and 0.0156% NaOCl and NaOBr as germicides were manufactured. 0.01 μl of microorganisms were inoculated on the media and cultured in 37 °C for 48 h. It was found that microorganisms did not grow in media with NaOCl and NaOBr concentration of 0.0625% and higher. Therefore, it can be suggested that in environments with pH value of 6 or lower, or NaOCl and NaOBr concentration of higher than 0.0625% suppresses microbial growth, thereby preventing microbial corrosion.

  16. Transition-metal prion protein attachment: Competition with copper

    NASA Astrophysics Data System (ADS)

    Hodak, Miroslav; Bernholc, Jerry

    2012-02-01

    Prion protein, PrP, is a protein capable of binding copper ions in multiple modes depending on their concentration. Misfolded PrP is implicated in a group of neurodegenerative diseases, which include ``mad cow disease'' and its human form, variant Creutzfeld-Jacob disease. An increasing amount of evidence suggests that attachment of non-copper metal ions to PrP triggers transformations to abnormal forms similar to those observed in prion diseases. In this work, we use hybrid Kohn-Sham/orbital-free density functional theory simulations to investigate copper replacement by other transition metals that bind to PrP, including zinc, iron and manganese. We consider all known copper binding modes in the N-terminal domain of PrP. Our calculations identify modes most susceptible to copper replacement and reveal metals that can successfully compete with copper for attachment to PrP.

  17. 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.

  18. 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

  19. 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

  20. L-threo-dihydroxyphenylserine corrects neurochemical abnormalities in a Menkes disease mouse model.

    PubMed

    Donsante, Anthony; Sullivan, Patricia; Goldstein, David S; Brinster, Lauren R; Kaler, Stephen G

    2013-02-01

    Menkes disease is a lethal neurodegenerative disorder of infancy caused by mutations in a copper-transporting adenosine triphosphatase gene, ATP7A. Among its multiple cellular tasks, ATP7A transfers copper to dopamine beta hydroxylase (DBH) within the lumen of the Golgi network or secretory granules, catalyzing the conversion of dopamine to norepinephrine. In a well-established mouse model of Menkes disease, mottled-brindled (mo-br), we tested whether systemic administration of L-threo-dihydroxyphenylserine (L-DOPS), a drug used successfully to treat autosomal recessive norepinephrine deficiency, would improve brain neurochemical abnormalities and neuropathology. At 8, 10, and 12 days of age, wild-type and mo-br mice received intraperitoneal injections of 200μg/g body weight of L-DOPS, or mock solution. Five hours after the final injection, the mice were euthanized, and brains were removed. We measured catecholamine metabolites affected by DBH via high-performance liquid chromatography with electrochemical detection, and assessed brain histopathology. Compared to mock-treated controls, mo-br mice that received intraperitoneal L-DOPS showed significant increases in brain norepinephrine (p < 0.001) and its deaminated metabolite, dihydroxyphenylglycol (p < 0.05). The ratio of a non-beta-hydroxylated metabolite in the catecholamine biosynthetic pathway, dihydroxyphenylacetic acid, to the beta-hydroxylated metabolite, dihydroxyphenylglycol, improved equivalently to results obtained previously with brain-directed ATP7A gene therapy (p < 0.01). However, L-DOPS treatment did not arrest global brain pathology or improve somatic growth, as gene therapy had. We conclude that (1) L-DOPS crosses the blood-brain barrier in mo-br mice and corrects brain neurochemical abnormalities, (2) norepinephrine deficiency is not the cause of neurodegeneration in mo-br mice, and (3) L-DOPS treatment may ameliorate noradrenergic hypofunction in Menkes disease. Copyright © 2012 American Neurological Association.

  1. L-DOPS corrects neurochemical abnormalities in a Menkes disease mouse model

    PubMed Central

    Donsante, Anthony; Sullivan, Patricia; Goldstein, David S.; Brinster, Lauren R.; Kaler, Stephen G.

    2012-01-01

    Objective Menkes disease is a lethal neurodegenerative disorder of infancy caused by mutations in a copper-transporting ATPase gene, ATP7A. Among its multiple cellular tasks, ATP7A transfers copper to dopamine-beta-hydroxylase (DBH) within the lumen of the Golgi network or secretory granules, catalyzing the conversion of dopamine to norepinephrine. In a well-established mouse model of Menkes disease, mottled-brindled, we tested whether systemic administration of L-threo-dihydroxyphenylserine (L-DOPS), a drug used successfully to treat autosomal recessive norepinephrine deficiency, would improve brain neurochemical abnormalities and neuropathology. Methods At 8, 10, and 12 days of age, wild type and mo-br mice received intraperi-toneal injections of 200μg/g body weight of L-DOPS, or mock solution. Five hours after the final injection, the mice were euthanized and brains removed. We measured catecholamine metabolites affected by DBH via high-performance liquid chromatography with electrochemical detection, and assessed brain histopathology. Results Compared to mock-treated controls, mo-br mice that received intraperitoneal L-DOPS showed significant increases in brain norepinephrine (P<0.001) and its deaminated metabolite, dihydroxyphenylglycol (DHPG, P<0.05). The ratio of a non-beta-hydroxylated metabolite in the catecholamine biosynthetic pathway, dihydroxyphenylacetic acid, to the beta-hydroxylated metabolite, dihydroxyphenylglycol, improved equivalently to results obtained previously with brain-directed ATP7A gene therapy (P<0.01). However, L-DOPS treatment did not arrest global brain pathology or improve somatic growth, as gene therapy had. Interpretation We conclude that 1) L-DOPS crosses the blood-brain barrier in mo-br mice and corrects brain neurochemical abnormalities, 2) norepinephrine deficiency is not the cause of neurodegeneration in mo-br mice, and 3) L-DOPS treatment may ameliorate noradrenergic hypofunction in Menkes disease. PMID:23224983

  2. Mechanism of Copper Uptake from Blood Plasma Ceruloplasmin by Mammalian Cells

    PubMed Central

    Ramos, Danny; Vargas, Rebecca; Gaite, Michaella; Montgomery, Aaron; Linder, Maria C.

    2016-01-01

    Ceruloplasmin, the main copper binding protein in blood plasma, has been of particular interest for its role in efflux of iron from cells, but has additional functions. Here we tested the hypothesis that it releases its copper for cell uptake by interacting with a cell surface reductase and transporters, producing apoceruloplasmin. Uptake and transepithelial transport of copper from ceruloplasmin was demonstrated with mammary epithelial cell monolayers (PMC42) with tight junctions grown in bicameral chambers, and purified human 64Cu-labeled ceruloplasmin secreted by HepG2 cells. Monolayers took up virtually all the 64Cu over 16h and secreted half into the apical (milk) fluid. This was partly inhibited by Ag(I). The 64Cu in ceruloplasmin purified from plasma of 64Cu-injected mice accumulated linearly in mouse embryonic fibroblasts (MEFs) over 3-6h. Rates were somewhat higher in Ctr1+/+ versus Ctr1-/- cells, and 3-fold lower at 2°C. The ceruloplasmin-derived 64Cu could not be removed by extensive washing or trypsin treatment, and most was recovered in the cytosol. Actual cell copper (determined by furnace atomic absorption) increased markedly upon 24h exposure to holoceruloplasmin. This was accompanied by a conversion of holo to apoceruloplasmin in the culture medium and did not occur during incubation in the absence of cells. Four different endocytosis inhibitors failed to prevent 64Cu uptake from ceruloplasmin. High concentrations of non-radioactive Cu(II)- or Fe(III)-NTA (substrates for cell surface reductases), or Cu(I)-NTA (to compete for transporter uptake) almost eliminated uptake of 64Cu from ceruloplasmin. MEFs had cell surface reductase activity and expressed Steap 2 (but not Steaps 3 and 4 or dCytB). However, six-day siRNA treatment was insufficient to reduce activity or uptake. We conclude that ceruloplasmin is a circulating copper transport protein that may interact with Steap2 on the cell surface, forming apoceruloplasmin, and Cu(I) that enters cells through CTR1 and an unknown copper uptake transporter. PMID:26934375

  3. Plasma vapor deposited n-indium tin oxide/p-copper indium oxide heterojunctions for optoelectronic device applications

    NASA Astrophysics Data System (ADS)

    Jaya, T. P.; Pradyumnan, P. P.

    2017-12-01

    Transparent crystalline n-indium tin oxide/p-copper indium oxide diode structures were fabricated on quartz substrates by plasma vapor deposition using radio frequency (RF) magnetron sputtering. The p-n heterojunction diodes were highly transparent in the visible region and exhibited rectifying current-voltage (I-V) characteristics with a good ideality factor. The sputter power during fabrication of the p-layer was found to have a profound effect on I-V characteristics, and the diode with the p-type layer deposited at a maximum power of 200 W exhibited the highest value of the diode ideality factor (η value) of 2.162, which suggests its potential use in optoelectronic applications. The ratio of forward current to reverse current exceeded 80 within the range of applied voltages of -1.5 to +1.5 V in all cases. The diode structure possessed an optical transmission of 60-70% in the visible region.

  4. 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.

  5. The Extracellular Domain of Human High Affinity Copper Transporter (hNdCTR1), Synthesized by E. coli Cells, Chelates Silver and Copper Ions In Vivo

    PubMed Central

    Sankova, Tatiana P.; Orlov, Iurii A.; Saveliev, Andrey N.; Kirilenko, Demid A.; Babich, Polina S.; Brunkov, Pavel N.; Puchkova, Ludmila V.

    2017-01-01

    There is much interest in effective copper chelators to correct copper dyshomeostasis in neurodegenerative and oncological diseases. In this study, a recombinant fusion protein for expression in Escherichia coli cells was constructed from glutathione-S-transferase (GST) and the N-terminal domain (ectodomain) of human high affinity copper transporter CTR1 (hNdCTR1), which has three metal-bound motifs. Several biological properties of the GST-hNdCTR1 fusion protein were assessed. It was demonstrated that in cells, the protein was prone to oligomerization, formed inclusion bodies and displayed no toxicity. Treatment of E. coli cells with copper and silver ions reduced cell viability in a dose- and time-dependent manner. Cells expressing GST-hNdCTR1 protein demonstrated resistance to the metal treatments. These cells accumulated silver ions and formed nanoparticles that contained AgCl and metallic silver. In this bacterial population, filamentous bacteria with a length of about 10 µm were often observed. The possibility for the fusion protein carrying extracellular metal binding motifs to integrate into the cell’s copper metabolism and its chelating properties are discussed. PMID:29099786

  6. The Extracellular Domain of Human High Affinity Copper Transporter (hNdCTR1), Synthesized by E. coli Cells, Chelates Silver and Copper Ions In Vivo.

    PubMed

    Sankova, Tatiana P; Orlov, Iurii A; Saveliev, Andrey N; Kirilenko, Demid A; Babich, Polina S; Brunkov, Pavel N; Puchkova, Ludmila V

    2017-11-03

    There is much interest in effective copper chelators to correct copper dyshomeostasis in neurodegenerative and oncological diseases. In this study, a recombinant fusion protein for expression in Escherichia coli cells was constructed from glutathione-S-transferase (GST) and the N-terminal domain (ectodomain) of human high affinity copper transporter CTR1 (hNdCTR1), which has three metal-bound motifs. Several biological properties of the GST-hNdCTR1 fusion protein were assessed. It was demonstrated that in cells, the protein was prone to oligomerization, formed inclusion bodies and displayed no toxicity. Treatment of E. coli cells with copper and silver ions reduced cell viability in a dose- and time-dependent manner. Cells expressing GST-hNdCTR1 protein demonstrated resistance to the metal treatments. These cells accumulated silver ions and formed nanoparticles that contained AgCl and metallic silver. In this bacterial population, filamentous bacteria with a length of about 10 µm were often observed. The possibility for the fusion protein carrying extracellular metal binding motifs to integrate into the cell's copper metabolism and its chelating properties are discussed.

  7. Removal of copper ions from aqueous solutions by means of micellar-enhanced ultrafiltration

    NASA Astrophysics Data System (ADS)

    Kowalska, Izabela; Klimonda, Aleksandra

    2017-11-01

    The aim of the study was to assess the usefulness of micellar-enhanced ultrafiltration (MEUF) for removal of copper ions from water solutions in comparison with classic ultrafiltration process. The tests were conducted in a semi-pilot membrane installation with the use of ultrafiltration module KOCH/ROMICON® at a transmembrane pressure of 0.05 MPa. The effect of concentration of copper ions on ultrafiltration process efficiency was investigated. The second part of the tests concerned the removal of copper ions by MEUF under wide range of anionic surfactant concentration (0.25, 1, and 5 CMC (critical micelle concentration)). Concentration of copper ions in model solutions was equal to 5, 20, and 50 mg Cu/L. Furthermore, the effect of surfactant leakage to the permeate side during filtration was evaluated. Conducted experiments confirmed effectiveness of MEUF in copper ions removal. For the highest copper concentration in the feed (i.e. 50 mg/L), the average concentration of copper ions in the permeate ranged from 1.2-4.7 mg Cu/L depending on surfactant concentration. During filtration experiments, UF module exhibited stable transport properties for model solutions containing copper. For the highest concentration of metal, the decrease of permeate flux did not exceed 11% after 60 minutes of filtration. In the presence of the surfactant, a slight deterioration of transport properties was observed.

  8. 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

  9. Copper-Catalysed Aminoboration of Vinylarenes with Hydroxylamine Esters-A Computational Mechanistic Study.

    PubMed

    Tobisch, Sven

    2017-12-14

    An in-depth computational probe of the copper-mediated formal aminoboration of β-alkylstyrenes with bis(pinacolato)diboron B 2 pin 2 and an archetype hydroxylamine ester by a dppbz-ligated {P^P}Cu I boryl catalyst (dppbz≡{P^P}≡1,2-bis(diphenylphosphino)benzene) is presented. This first comprehensive computational study of the copper-mediated formal aminoboration utilising an electrophilic strategy has identified the most accessible pathway for productive catalysis. The mechanistic picture derived from smooth energy profiles acquired by employing a reliable computational protocol applied to a realistic catalyst model conforms to all available experimental data. The high degree of regio- and stereoselectivity achieved in syn-borylcupration and Umpolung electrophilic amination is instrumental to the exclusive generation of the (syn)-β-aminoalkylborane product. On the one hand, syn-borylcupration furnishes exclusively β-borylalkylcopper nucleophile upon boryl addition onto the vinylarene β-carbon. Its subsequent approach by the hydroxylamine electrophile to deliver the product with the release of {P^P}Cu I benzoate favours a stepwise stereoretentive S N 2-type oxidative addition/N-C bond-forming reductive elimination sequence. The copper benzoate species represents the catalyst resting state, and its transformation into the catalytically active borylcopper species upon salt metathesis with Li(OtBu) base and transmetallation with B 2 pin 2 is turnover limiting. Electronically modified β-alkylstyrenes featuring a para-CF 3 substituted phenyl ring render the borylcupration faster, and more electron-rich hydroxylamine agents decelerate the electrophilic amination. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Emergency contraception with a Copper IUD or oral levonorgestrel: an observational study of 1-year pregnancy rates

    PubMed Central

    Turok, David K.; Jacobson, Janet C.; Dermish, Amna I.; Simonsen, Sara E.; Gurtcheff, Shawn; McFadden, Molly; Murphy, Patricia A.

    2014-01-01

    Objective We investigated the one-year pregnancy rates for emergency contraception (EC) users who selected the copper T380 IUD or oral levonorgestrel (LNG) for EC. Study Design This prospective study followed women for 1 year after choosing either the copper T380 IUD or oral LNG for EC. The study was powered to detect a 6% difference in pregnancy rates within the year after presenting for EC. Results Of the 542 women who presented for EC, agreed to participate in the trial, and meet inclusion criteria, 215 (40%) chose the copper IUD and 327 (60%) chose oral LNG. In the IUD group, 127 (59%) were nulligravid. IUD insertion failed in 42 women (19%). The 1-year follow-up rate was 443/542 (82%); 64% of IUD users contacted at 1 year still had their IUDs in place. The 1-year cumulative pregnancy rate in women choosing the IUD was 6.5% vs. 12.2% in those choosing oral LNG (HR= 0.53, 95% CI: 0.29–0.97, p=0.041). By type of EC method actually received, corresponding values were 5.2% for copper IUD users vs. 12.3% for oral LNG users, HR 0.42 (95% CI: 0.20–0.85, p= 0.017). A multivariable logistic regression model controlling for demographic variables demonstrates that women who chose the IUD for EC had fewer pregnancies in the following year than those who chose oral LNG (HR 0.50, 95% CI: 0.26–0.96, p=0.037). Conclusion One year after presenting for EC women choosing the copper IUD for EC were half as likely to have a pregnancy compared to those choosing oral LNG. PMID:24332433

  11. Phosphorus-Rich Copper Phosphide Nanowires for Field-Effect Transistors and Lithium-Ion Batteries.

    PubMed

    Li, Guo-An; Wang, Chiu-Yen; Chang, Wei-Chung; Tuan, Hsing-Yu

    2016-09-27

    Phosphorus-rich transition metal phosphide CuP2 nanowires were synthesized with high quality and high yield (∼60%) via the supercritical fluid-liquid-solid (SFLS) growth at 410 °C and 10.2 MPa. The obtained CuP2 nanowires have a high aspect ratio and exhibit a single crystal structure of monoclinic CuP2 without any impurity phase. CuP2 nanowires have progressive improvement for semiconductors and energy storages compared with bulk CuP2. Being utilized for back-gate field effect transistor (FET) measurement, CuP2 nanowires possess a p-type behavior intrinsically with an on/off ratio larger than 10(4) and its single nanowire electrical transport property exhibits a hole mobility of 147 cm(2) V(-1) s(-1), representing the example of a CuP2 transistor. In addition, CuP2 nanowires can serve as an appealing anode material for a lithium-ion battery electrode. The discharge capacity remained at 945 mA h g(-1) after 100 cycles, showing a good capacity retention of 88% based on the first discharge capacity. Even at a high rate of 6 C, the electrode still exhibited an outstanding result with a capacity of ∼600 mA h g(-1). Ex-situ transmission electron microscopy and CV tests demonstrate that the stability of capacity retention and remarkable rate capability of the CuP2 nanowires electrode are attributed to the role of the metal phosphide conversion-type lithium storage mechanism. Finally, CuP2 nanowire anodes and LiFePO4 cathodes were assembled into pouch-type lithium batteries offering a capacity over 60 mA h. The full cell shows high capacity and stable capacity retention and can be used as an energy supply to operate electronic devices such as mobile phones and mini 4WD cars.

  12. Silencing the Menkes Copper-Transporting ATPase (Atp7a) Gene in Rat Intestinal Epithelial (IEC-6) Cells Increases Iron Flux via Transcriptional Induction of Ferroportin 1 (Fpn1)123

    PubMed Central

    Gulec, Sukru; Collins, James F.

    2014-01-01

    The Menkes copper-transporting ATPase (Atp7a) gene is induced in rat duodenum during iron deficiency, consistent with copper accumulation in the intestinal mucosa and liver. To test the hypothesis that ATP7A influences intestinal iron metabolism, the Atp7a gene was silenced in rat intestinal epithelial (IEC-6) cells using short hairpin RNA (shRNA) technology. Perturbations in intracellular copper homeostasis were noted in knockdown cells, consistent with the dual roles of ATP7A in pumping copper into the trans-Golgi (for cuproenzyme synthesis) and exporting copper from cells. Intracellular iron concentrations were unaffected by Atp7a knockdown. Unexpectedly, however, vectorial iron (59Fe) transport increased (∼33%) in knockdown cells grown in bicameral inserts and increased further (∼70%) by iron deprivation (compared with negative control shRNA-transfected cells). Additional experiments were designed to elucidate the molecular mechanism of increased transepithelial iron flux. Enhanced iron uptake by knockdown cells was associated with increased expression of a ferrireductase (duodenal cytochrome b) and activity of a cell-surface ferrireductase. Increased iron efflux from knockdown cells was likely mediated via transcriptional activation of the ferroportin 1 gene (by an unknown mechanism). Moreover, Atp7a knockdown significantly attenuated expression of an iron oxidase [hephaestin (HEPH); by ∼80%] and membrane ferroxidase activity (by ∼50%). Cytosolic ferroxidase activity, however, was retained in knockdown cells (75% of control cells), perhaps compensating for diminished HEPH activity. This investigation has thus documented alterations in iron homeostasis associated with Atp7a knockdown in enterocyte-like cells. Alterations in copper transport, trafficking, or distribution may underlie the increase in transepithelial iron flux noted when ATP7A activity is diminished. PMID:24174620

  13. Time evolution of the general characteristics and Cu retention capacity in an acid soil amended with a bentonite winery waste.

    PubMed

    Fernández-Calviño, David; Rodríguez-Salgado, Isabel; Pérez-Rodríguez, Paula; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel

    2015-03-01

    The effect of bentonite waste added to a "poor" soil on its general characteristic and copper adsorption capacity was assessed. The soil was amended with different bentonite waste concentrations (0, 10, 20, 40 and 80 Mg ha(-1)) in laboratory pots, and different times of incubation of samples were tested (one day and one, four and eight months). The addition of bentonite waste increased the pH, organic matter content and phosphorus and potassium concentrations in the soil, being stable for P and K, whereas the organic matter decreased with time. Additionally, the copper sorption capacity of the soil and the energy of the Cu bonds increased with bentonite waste additions. However, the use of this type of waste in soil presented important drawbacks for waste dosages higher than 20 Mg ha(-1), such as an excessive increase of the soil pH and an increase of copper in the soil solution. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2018-01-01

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

  15. 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.

  16. Fate and transport with material response characterization of green sorption media for copper removal via adsorption process.

    PubMed

    Chang, Ni-Bin; Houmann, Cameron; Lin, Kuen-Song; Wanielista, Martin

    2016-02-01

    Green adsorption media with the inclusion of renewable and recycled materials can be applied as a stormwater best management practice for copper removal. A green adsorption media mixture composed of recycled tire chunk, expanded clay aggregate, and coconut coir was physicochemically evaluated for its potential use in an upflow media filter. A suite of tests were conducted on the media mixture and the individual media components including studies of particle size distribution, isotherms, column adsorption and reaction kinetics. Isotherm test results revealed that the coconut coir had the highest affinity for copper (q(max) = 71.1 mg g(-1)), and that adsorption was maximized at a pH of 7.0. The coconut coir also performed the best under dynamic conditions, having an equilibrium uptake of 1.63 mg g(-1). FE-SEM imaging found a strong correlation between the porosity of the micro pore structure and the adsorptive capacity. The use of the green adsorption media mixture in isolation or the coconut coir with an expanded clay filtration chamber could be an effective and reliable stormwater best management practice for copper removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Copper oxide thin films anchored on glass substrate by sol gel spin coating technique

    NASA Astrophysics Data System (ADS)

    Krishnaprabha, M.; Venu, M. Parvathy; Pattabi, Manjunatha

    2018-05-01

    Owing to the excellent optical, thermal, electrical and photocatalytic properties, copper oxide nanoparticles/films have found applications in optoelectronic devices like solar/photovoltaic cells, lithium ion batteries, gas sensors, catalysts, magnetic storage media etc. Copper oxide is a p-type semiconductor material having a band gap energy varying from 1.2 eV-2.1 eV. Syzygium Samarangense fruit extract was used as reducing agent to synthesize copper oxide nanostructures at room temperature from 10 mM copper sulphate pentahydrate solution. The synthesized nanostructures are deposited onto glass substrate by spin coating followed by annealing the film at 200 °C. Both the copper oxide colloid and films are characterized using UV-Vis spectroscopy, field emission scanning electron microscopy (FESEM) and energy dispersive spectroscopy (EDS) techniques. Presence of 2 peaks at 500 nm and a broad peak centered around 800 nm in the UV-Vis absorbance spectra of copper oxide colloid/films is indicative of the formation of anisotropic copper oxide nanostructures is confirmed by the FESEM images which showed the presence of triangular shaped and rod shaped particles. The rod shaped particles inside island like structures were found in unannealed films whereas the annealed films contained different shaped particles with reduced sizes. The elemental analysis using EDS spectra of copper oxide nanoparticles/films showed the presence of both copper and oxygen. Electrical properties of copper oxide nanoparticles are affected due to quantum size effect. The electrical studies carried out on both unannealed and annealed copper oxide films revealed an increase in resistivity with annealing of the films.

  18. The T1048I mutation in ATP7A gene causes an unusual Menkes disease presentation

    PubMed Central

    2012-01-01

    Background The ATP7A gene encodes the ATP7A protein, which is a trans-Golgi network copper transporter expressed in the brain and other organs. Mutations in this gene cause disorders of copper metabolism, such as Menkes disease. Here we describe the novel and unusual mutation (p.T1048I) in the ATP7A gene of a child with Menkes disease. The mutation affects a conserved DKTGT1048 phosphorylation motif that is involved in the catalytic activity of ATP7A. We also describe the clinical course and the response to copper treatment in this patient. Case presentation An 11-month-old male Caucasian infant was studied because of hypotonia, ataxia and global developmental delay. The patient presented low levels of serum copper and ceruloplasmin, and was shown to be hemizygous for the p.T1048I mutation in ATP7A. The diagnosis was confirmed when the patient was 18 months old, and treatment with copper-histidinate (Cu-His) was started immediately. The patient showed some neurological improvement and he is currently 8 years old. Because the p.T1048I mutation affects its catalytic site, we expected a complete loss of functional ATP7A and a classical Menkes disease presentation. However, the clinical course of the patient was mild, and he responded to Cu-His treatment, which suggests that this mutation leads to partial conservation of the activity of ATP7A. Conclusion This case emphasizes the important correlation between genotype and phenotype in patients with Menkes disease. The prognosis in Menkes disease is associated with early detection, early initiation of treatment and with the preservation of some ATP7A activity, which is necessary for Cu-His treatment response. The description of this new mutation and the response of the patient to Cu-His treatment will contribute to the growing body of knowledge about treatment response in Menkes disease. PMID:22992316

  19. 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

  20. Thermoelectric Study of Copper Selenide

    NASA Astrophysics Data System (ADS)

    Yao, Mengliang; Liu, Weishu; Ren, Zhifeng; Opeil, Cyril

    2014-03-01

    Nanostructuring has been shown to be an effective approach in reducing lattice thermal conductivity and improving the figure of merit of thermoelectric materials. Copper selenide is a layered structure material, which has a low thermal conductivity and p-type Seebeck coefficient at low temperatures. We have evaluated several hot-pressed, nanostructured copper selenide samples with different dopants for their thermoelectric properties. The phenomenon of the charge-density wave observed in the nanocomposite, resistivity, Seebeck, thermal conductivity and carrier mobility will be discussed. Funding for this research was provided by the Solid State Solar - Thermal Energy Conversion Center (S3TEC), an Energy Frontier Research Center sponsored by the DOE, Office of Basic Energy Science, Award No. DE-SC0001299/ DE-FG02-09ER46577.

  1. Copper interstitial recombination centers in Cu3N

    NASA Astrophysics Data System (ADS)

    Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; Hanifi, David; Salleo, Alberto; Magyari-Köpe, Blanka; Nishi, Yoshio; Bent, Stacey F.; Clemens, Bruce M.

    2018-06-01

    We present a comprehensive study of the earth-abundant semiconductor Cu3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies VCu have shallow defect levels while copper interstitials Cui behave as deep potential wells in the conduction band, which mediate Shockley-Read-Hall recombination. The existence of Cui defects has been experimentally verified using photothermal deflection spectroscopy. A Cu3N /ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. The absence of photocurrent can be explained by a large concentration of Cui recombination centers capturing electrons in p -type Cu3N .

  2. Influence of oxygen, albumin and pH on copper dissolution in a simulated uterine fluid.

    PubMed

    Bastidas, D M; Cano, E; Mora, E M

    2005-06-01

    The aim of this paper is to study the influence of albumin content, from 5 to 45 g/L, on copper dissolution and compounds composition in a simulated uterine solution. Experiments were performed in atmospheric pressure conditions and with an additional oxygen pressure of 0.2 atmospheres, at 6.3 and 8.0 pH values, and at a temperature of 37 +/- 0.1 degrees C for 1, 3, 7, and 30 days experimentation time. The copper dissolution rate has been determined using absorbance measurements, finding the highest value for pH 8.0, 35 g/L albumin, and with an additional oxygen pressure of 0.2 atmospheres: 674 microg/day for 1 day, and 301 microg/day for 30 days. X-ray photoelectron spectroscopy (XPS) results show copper(II) as the main copper oxidation state at pH 8.0; and copper(I) and metallic copper at pH 6.3. The presence of albumin up to 35 g/L, accelerates copper dissolution. For high albumin content a stabilisation on the copper dissolution takes place. Corrosion product layer morphology is poorly protective, showing paths through which copper ions can release.

  3. Transport and spatial energy deposition of relativistic electrons in copper-doped fast ignition plasmas

    DOE PAGES

    Jarrott, L. C.; McGuffey, C.; Beg, F. N.; ...

    2017-10-24

    Fast electron transport and spatial energy deposition are investigated in integrated cone-guided Fast Ignition experiments by measuring fast electron induced copper K-shell emission using a copper tracer added to deuterated plastic shells with a geometrically reentrant gold cone. Experiments were carried out at the Laboratory for Laser Energetics on the OMEGA/OMEGA-EP Laser where the plastic shells were imploded using 54 of the 60 OMEGA60 beams (3ω, 20 kJ), while the high intensity OMEGA-EP (BL2) beam (1 ω, 10 ps, 500 J, I peak > 10 19 W/cm 2) was focused onto the inner cone tip. Here, a retrograde analysis usingmore » the hybrid-PIC electron transport code, ZUMA, is performed to examine the sensitivity of the copper Kα spatial profile on the laser-produced fast electrons, facilitating the optimization of new target point designs and laser configurations to improve the compressed core areal density by a factor of 4 and the fast electron energy coupling by a factor of 3.5.« less

  4. Medicago truncatula copper transporter 1 (MtCOPT1) delivers copper for symbiotic nitrogen fixation.

    PubMed

    Senovilla, Marta; Castro-Rodríguez, Rosario; Abreu, Isidro; Escudero, Viviana; Kryvoruchko, Igor; Udvardi, Michael K; Imperial, Juan; González-Guerrero, Manuel

    2018-04-01

    Copper is an essential nutrient for symbiotic nitrogen fixation. This element is delivered by the host plant to the nodule, where membrane copper (Cu) transporter would introduce it into the cell to synthesize cupro-proteins. COPT family members in the model legume Medicago truncatula were identified and their expression determined. Yeast complementation assays, confocal microscopy and phenotypical characterization of a Tnt1 insertional mutant line were carried out in the nodule-specific M. truncatula COPT family member. Medicago truncatula genome encodes eight COPT transporters. MtCOPT1 (Medtr4g019870) is the only nodule-specific COPT gene. It is located in the plasma membrane of the differentiation, interzone and early fixation zones. Loss of MtCOPT1 function results in a Cu-mitigated reduction of biomass production when the plant obtains its nitrogen exclusively from symbiotic nitrogen fixation. Mutation of MtCOPT1 results in diminished nitrogenase activity in nodules, likely an indirect effect from the loss of a Cu-dependent function, such as cytochrome oxidase activity in copt1-1 bacteroids. These data are consistent with a model in which MtCOPT1 transports Cu from the apoplast into nodule cells to provide Cu for essential metabolic processes associated with symbiotic nitrogen fixation. © 2018 The Authors. New Phytologist © 2018 New Phytologist Trust.

  5. The P-type ATPase CtpG preferentially transports Cd2+ across the Mycobacterium tuberculosis plasma membrane.

    PubMed

    López, Marcela; Quitian, Laudy-Viviana; Calderón, Martha-Nancy; Soto, Carlos-Y

    2018-04-01

    P 1B -type ATPases are involved in heavy metal transport across the plasma membrane. Some Mycobacterium tuberculosis P-type ATPases are induced during infection, suggesting that this type of transporter could play a critical role in mycobacterial survival. To date, the ion specificity of M. tuberculosis heavy metal-transporting P 1B -ATPases is not well understood. In this work, we observed that, although divalent heavy metal cations such as Cu 2+ , Co 2+ , Ni 2+ , Zn 2+ Cd 2+ and Pb 2+ stimulate the ATPase activity of the putative P 1B -type ATPase CtpG in the plasma membrane, whole cells of M. smegmatis expressing CtpG only tolerate high levels of Cd 2+ and Cu 2+ . As indicator of the catalytic constant, Michaelis-Menten kinetics showed that CtpG embedded in the mycobacterial cell membrane has a V max /K m ratio 7.4-fold higher for Cd 2+ than for Cu 2+ ions. Thus, although CtpG can accept different substrates in vitro, this P-type ATPase transports Cd 2+ more efficiently than other heavy metal cations across the mycobacterial plasma membrane.

  6. Advanced Copper Composites Against Copper-Tolerant Xanthomonas perforans and Tomato Bacterial Spot.

    PubMed

    Strayer-Scherer, A; Liao, Y Y; Young, M; Ritchie, L; Vallad, G E; Santra, S; Freeman, J H; Clark, D; Jones, J B; Paret, M L

    2018-02-01

    Bacterial spot, caused by Xanthomonas spp., is a widespread and damaging bacterial disease of tomato (Solanum lycopersicum). For disease management, growers rely on copper bactericides, which are often ineffective due to the presence of copper-tolerant Xanthomonas strains. This study evaluated the antibacterial activity of the new copper composites core-shell copper (CS-Cu), multivalent copper (MV-Cu), and fixed quaternary ammonium copper (FQ-Cu) as potential alternatives to commercially available micron-sized copper bactericides for controlling copper-tolerant Xanthomonas perforans. In vitro, metallic copper from CS-Cu and FQ-Cu at 100 μg/ml killed the copper-tolerant X. perforans strain within 1 h of exposure. In contrast, none of the micron-sized copper rates (100 to 1,000 μg/ml) from Kocide 3000 significantly reduced copper-tolerant X. perforans populations after 48 h of exposure compared with the water control (P < 0.05). All copper-based treatments killed the copper-sensitive X. perforans strain within 1 h. Greenhouse studies demonstrated that all copper composites significantly reduced bacterial spot disease severity when compared with copper-mancozeb and water controls (P < 0.05). Although there was no significant impact on yield, copper composites significantly reduced disease severity when compared with water controls, using 80% less metallic copper in comparison with copper-mancozeb in field studies (P < 0.05). This study highlights the discovery that copper composites have the potential to manage copper-tolerant X. perforans and tomato bacterial spot.

  7. Fast reduction of a copper center in laccase by nitric oxide and formation of a peroxide intermediate.

    PubMed

    Torres, Jaume; Svistunenko, Dimitri; Karlsson, Bo; Cooper, Chris E; Wilson, Michael T

    2002-02-13

    The rapid reduction of one of the copper atoms (type 2) of tree laccase by nitric oxide (NO) has been detected. Addition of NO to native laccase in the presence of oxygen leads to EPR changes consistent with fast reduction and slow reoxidation of this metal center. These events are paralleled by optical changes that are reminiscent of formation and decay of the peroxide intermediate in a fraction of the enzyme population. Formation of this species is only possible if the trinuclear copper cluster (type 2 plus type 3) is fully reduced. This condition can only be met if, as suggested previously, a fraction of the enzyme contains both type 3 coppers already reduced before addition of NO. Our data are consistent with this assumption. We have suggested recently that fast reduction of copper is the mechanism by which NO interacts with the oxidized dinuclear center in cytochrome c oxidase. The present experiments using laccase strongly support this view and suggest this reaction as a general mechanism by which copper proteins interact with NO. In addition, this provides an unexploited way to produce a stable peroxide intermediate in copper oxidases in which the full complement of copper atoms is present. This enables the O-O scission step in the catalytic cycle to be studied by electron addition to the peroxide derivative through the native electron entry site, type 1 copper.

  8. Geochemical characterization of shallow ground water in the Eutaw aquifer, Montgomery, Alabama

    USGS Publications Warehouse

    Robinson, J.L.; Journey, C.A.

    2004-01-01

    Ground water samples were collected from 30 wells located in, or directly down gradient from, recharge areas of the Eutaw aquifer in Montgomery, Alabama. The major ion content of the water evolves from calcium-sodium-chloride- dominated type in the recharge area to calcium-bicarbonate-dominated type in the confined portion of the aquifer. Ground water in the recharge area was undersaturated with respect to aluminosilicate and carbonate minerals. Ground water in the confined portion of the aquifer was at equilibrium levels for calcite and potassium feldspar. Dissolved oxygen and nitrite-plus-nitrate concentrations decreased as ground water age increased; pH, iron, and sulfate concentrations increased as ground water age increased. Aluminum, copper, and zinc concentrations decreased as ground water age and pH increased. These relations indicate that nitrate, aluminum, copper, and zinc are removed from solution as water moves from recharge areas to the confined areas of the Eutaw aquifer. The natural evolution of ground water quality, which typically increases the pH and decreases the dissolved oxygen content, may be an important limiting factor to the migration of nitrogen based compounds and metals.

  9. Mobility of nutrients and trace metals during weathering in the late Archean

    NASA Astrophysics Data System (ADS)

    Hao, Jihua; Sverjensky, Dimitri A.; Hazen, Robert M.

    2017-08-01

    The evolution of the geosphere and biosphere depends on the availability of bio-essential nutrients and trace metals. Consequently, the chemical and isotopic variability of trace elements in the sedimentary record have been widely used to infer the existence of early life and fluctuations in the near-surface environment on the early Earth, particularly fluctuations in the redox state of the atmosphere. In this study, we applied late Archean weathering models (Hao et al., 2017), developed to estimate the behavior of major elements and the composition of late Archean world average river water, to explore the behavior of nutrient and trace metals and their potential for riverine transport. We focused on P, Mn, Cr, and Cu during the weathering of olivine basalt. In our standard late Archean weathering model (pCO2,g = 10-1.5 bars, pH2,g = 10-5.0 bars), crustal apatite was totally dissolved by the acidic rainwater during weathering. Our model quantitatively links the pCO2,g of the atmosphere to phosphate levels transported by rivers. The development of late Archean river water (pH = 6.4) resulted in riverine phosphate of at least 1.7 μmolar, much higher than at the present-day. At the end of the early Proterozoic snowball Earth event when pCO2,g could be 0.01-0.10 bars, river water may have transported up to 70 μmolar phosphate, depending on the availability of apatite, thereby stimulating high levels of oxygenic photosynthesis in the marine environment. Crustal levels of Mn in olivine dissolved completely during weathering, except at large extents of weathering where Mn was stored as a component of a secondary carbonate mineral. The corresponding Mn content of river water, about 1.2 μmolar, is higher than in modern river water. Whiffs of 10-5 mole O2 gas or HNO3 kg-1 H2O resulted in the formation of pyrolusite (MnO2) and abundant hematite and simultaneous dramatic decreases in the concentration of Mn(II) in the river water. Chromite dissolution resulted in negligible dissolved Cr in Archean river water. However, amorphous Cr(OH)3 representing easily-weatherable Cr-bearing minerals dissolved totally during the weathering simulations, resulting in concentrations of Cr(III) in the river water of up to 0.14 μmolar, higher than at the present-day. Late Archean weathering of accessory chalcopyrite produced chalcocite and bornite, and extremely low concentrations of Cu (<10-15 molar) because of the low solubilities of the copper sulfides. However, pulses of either O2,g or HNO3 produced native copper, chalcocite, and bornite, much more hematite, and river water containing levels of dissolved Cu comparable to the present-day. Copper mineralogy predicted by weathering models might provide a new correlation with evidence from studies of copper mineral evolution. Overall, our results implied that the redox state of the atmosphere, the pH of surface waters, and the availability of easily-weatherable minerals are all important factors controlling the dissolution of trace elements in river water. Interpretation of the sedimentary signatures of trace elements should consider not only the redox state but also the pH and availability of accessory minerals.

  10. A coupled hydrodynamic-hydrochemical modeling for predicting mineral transport in a natural acid drainage system.

    NASA Astrophysics Data System (ADS)

    Zegers Risopatron, G., Sr.; Navarro, L.; Montserrat, S., Sr.; McPhee, J. P.; Niño, Y.

    2017-12-01

    The geochemistry of water and sediments, coupled with hydrodynamic transport in mountainous channels, is of particular interest in central Chilean Andes due to natural occurrence of acid waters. In this paper, we present a coupled transport and geochemical model to estimate and understand transport processes and fate of minerals at the Yerba Loca Basin, located near Santiago, Chile. In the upper zone, water presentes low pH ( 3) and high concentrations of iron, aluminum, copper, manganese and zinc. Acidity and minerals are the consequence of water-rock interactions in hydrothermal alteration zones, rich in sulphides and sulphates, covered by seasonal snow and glaciers. Downstream, as a consequence of neutral to alkaline lateral water contributions (pH >7) along the river, pH increases and concentration of solutes decreases. The mineral transport model has three components: (i) a hydrodynamic model, where we use HEC-RAS to solve 1D Saint-Venant equations, (ii) a sediment transport model to estimate erosion and sedimentation rates, which quantify minerals transference between water and riverbed and (iii) a solute transport model, based on the 1D OTIS model which takes into account the temporal delay in solutes transport that typically is observed in natural channels (transient storage). Hydrochemistry is solved using PHREEQC, a software for speciation and batch reaction. Our results show that correlation between mineral precipitation and dissolution according to pH values changes along the river. Based on pH measurements (and according to literature) we inferred that main minerals in the water system are brochantite, ferrihydrite, hydrobasaluminite and schwertmannite. Results show that our model can predict the transport and fate of minerals and metals in the Yerba Loca Basin. Mineral dissolution and precipitation process occur for limited ranges of pH values. When pH values are increased, iron minerals (schwertmannite) are the first to precipitate ( 2.5

  11. Copper content in lake sediments as a tracer of urban emissions: evaluation through a source-transport-storage model.

    PubMed

    Cui, Qing; Brandt, Nils; Sinha, Rajib; Malmström, Maria E

    2010-06-01

    A coupled source-transport-storage model was developed to determine the origin and path of copper from materials/goods in use in the urban drainage area and the fate of copper in local recipient lakes. The model was applied and tested using five small lakes in Stockholm, Sweden. In the case of the polluted lakes Råcksta Träsk, Trekanten and Långsjön, the source strengths of copper identified by the model were found to be well linked with independently observed copper contents in the lake sediments through the model. The model results also showed that traffic emissions, especially from brake linings, dominated the total load in all five cases. Sequential sedimentation and burial proved to be the most important fate processes of copper in all lakes, except Råcksta Träsk, where outflow dominated. The model indicated that the sediment copper content can be used as a tracer of the urban diffuse copper source strength, but that the response to changes in source strength is fairly slow (decades). Major uncertainties in the source model were related to management of stormwater in the urban area, the rate of wear of brake linings and weathering of copper roofs. The uncertainty of the coupled model is in addition affected mainly by parameters quantifying the sedimentation and bury processes, such as particulate fraction, settling velocity of particles, and sedimentation rate. As a demonstration example, we used the model to predict the response of the sediment copper level to a decrease in the copper load from the urban catchment in one of the case study lakes. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  12. Copper transport and trafficking at the host-bacterial pathogen interface.

    PubMed

    Fu, Yue; Chang, Feng-Ming James; Giedroc, David P

    2014-12-16

    CONSPECTUS: The human innate immune system has evolved the means to reduce the bioavailability of first-row late d-block transition metal ions to invading microbial pathogens in a process termed "nutritional immunity". Transition metals from Mn(II) to Zn(II) function as metalloenzyme cofactors in all living cells, and the successful pathogen is capable of mounting an adaptive response to mitigate the effects of host control of transition metal bioavailability. Emerging evidence suggests that Mn, Fe, and Zn are withheld from the pathogen in classically defined nutritional immunity, while Cu is used to kill invading microorganisms. This Account summarizes new molecular-level insights into copper trafficking across cell membranes from studies of a number of important bacterial pathogens and model organisms, including Escherichia coli, Salmonella species, Mycobacterium tuberculosis, and Streptococcus pneumoniae, to illustrate general principles of cellular copper resistance. Recent highlights of copper chemistry at the host-microbial pathogen interface include the first high resolution structures and functional characterization of a Cu(I)-effluxing P1B-ATPase, a new class of bacterial copper chaperone, a fungal Cu-only superoxide dismutase SOD5, and the discovery of a small molecule Cu-bound SOD mimetic. Successful harnessing by the pathogen of host-derived bactericidal Cu to reduce the bacterial load of reactive oxygen species (ROS) is an emerging theme; in addition, recent studies continue to emphasize the importance of short lifetime protein-protein interactions that orchestrate the channeling of Cu(I) from donor to target without dissociation into bulk solution; this, in turn, mitigates the off-pathway effects of Cu(I) toxicity in both the periplasm in Gram negative organisms and in the bacterial cytoplasm. It is unclear as yet, outside of the photosynthetic bacteria, whether Cu(I) is trafficked to other cellular destinations, for example, to cuproenzymes or other intracellular storage sites, or the general degree to which copper chaperones vs copper efflux transporters are essential for bacterial pathogenesis in the vertebrate host. Future studies will be directed toward the identification and structural characterization of other cellular targets of Cu(I) trafficking and resistance, the physical and mechanistic characterization of Cu(I)-transfer intermediates, and elucidation of the mutual dependence of Cu(I) trafficking and cellular redox status on thiol chemistry in the cytoplasm. Crippling bacterial control of Cu(I) sensing, trafficking, and efflux may represent a viable strategy for the development of new antibiotics.

  13. Copper-containing plastocyanin used for electron transport by an oceanic diatom.

    PubMed

    Peers, Graham; Price, Neil M

    2006-05-18

    The supply of some essential metals to pelagic ecosystems is less than the demand, so many phytoplankton have slow rates of photosynthetic production and restricted growth. The types and amounts of metals required by phytoplankton depends on their evolutionary history and on their adaptations to metal availability, which varies widely among ocean habitats. Diatoms, for example, need considerably less iron (Fe) to grow than chlorophyll-b-containing taxa, and the oceanic species demand roughly one-tenth the amount of coastal strains. Like Fe, copper (Cu) is scarce in the open sea, but notably higher concentrations of it are required for the growth of oceanic than of coastal isolates. Here we report that the greater Cu requirement in an oceanic diatom, Thalassiosira oceanica, is entirely due to a single Cu-containing protein, plastocyanin, which--until now--was only known to exist in organisms with chlorophyll b and cyanobacteria. Algae containing chlorophyll c, including the closely related coastal species T. weissflogii, are thought to lack plastocyanin and contain a functionally equivalent Fe-containing homologue, cytochrome c6 (ref. 9). Copper deficiency in T. oceanica inhibits electron transport regardless of Fe status, implying a constitutive role for plastocyanin in the light reactions of photosynthesis in this species. The results suggest that selection pressure imposed by Fe limitation has resulted in the use of a Cu protein for photosynthesis in an oceanic diatom. This biochemical switch reduces the need for Fe and increases the requirement for Cu, which is relatively more abundant in the open sea.

  14. A tropical sediment toxicity test using the dipteran Chironomus crassiforceps to test metal bioavailability with sediment pH change in tropical acid-sulfate sediments.

    PubMed

    Peck, Mika R; Klessa, David A; Baird, Donald J

    2002-04-01

    The wetlands of the Magela floodplain of northern Australia, which is the major sink for dissolved metals transported in the Magela Creek system, contain acid-sulfate sediments. The rewetting of oxidized acid-sulfate soil each wet season produces acidic pulses that have the potential to alter the bioavailability of sediment-associated metal contaminants. Acute toxicity tests (72-h mean lethal concentration [LC50]) using the tropical chironomid Chironomus crassiforceps Kieffer showed that copper toxicity decreased from 0.64 mg/L at pH 6 to 2.30 mg/L at pH 4. Uranium toxicity showed a similar trend (36 mg/L at pH 6 and 58 mg/L at pH 4). Sediment toxicity tests developed using C. crassiforceps also showed that both metals were less toxic at the lower sediment pH with pore-water copper toxicity having a lowest-observed-effect concentration of 4.73 mg/L at pH 4 compared to 1.72 mg/L at pH 6. However, a lower pH increased pore-water metal concentrations and overlying water concentrations in bioassays. Hydrogen ion competition on metal receptor sites in C. crassiforceps was proposed to explain the decrease in toxicity in response to increased H+ activity. This study highlights the need to consider site-specific physicochemical conditions before applying generic risk assessment methods.

  15. Feed gas contaminant control in ion transport membrane systems

    DOEpatents

    Carolan, Michael Francis [Allentown, PA; Minford, Eric [Laurys Station, PA; Waldron, William Emil [Whitehall, PA

    2009-07-07

    Ion transport membrane oxidation system comprising an enclosure having an interior and an interior surface, inlet piping having an internal surface and adapted to introduce a heated feed gas into the interior of the enclosure, and outlet piping adapted to withdraw a product gas from the interior of the enclosure; one or more planar ion transport membrane modules disposed in the interior of the enclosure, each membrane module comprising mixed metal oxide material; and a preheater adapted to heat a feed gas to provide the heated feed gas to the inlet piping, wherein the preheater comprises an interior surface. Any of the interior surfaces of the enclosure, the inlet piping, and the preheater may be lined with a copper-containing metal lining. Alternatively, any of the interior surfaces of the inlet piping and the preheater may be lined with a copper-containing metal lining and the enclosure may comprise copper.

  16. Influence of electrochemical potential on the displacement of aqueous electrolyte from a copper surface by oil

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

    Kendig, M.W.; Fadner, T.A.

    1985-02-01

    The forces responsible for the meniscus formed during the dynamic displacement of a 0.1 M H/sub 3/BO/sub 3/ + 0.5 M NaClO/sub 4/ solution by oil from a copper surface depend on the electrochemical potential of the copper and on an active component in the oil. For a nonpolar mineral oil containing oleic acid, a negative potential applied to copper produces hydrophilic behavior of the copper surface in the aqueous phase. This result is attribute largely to electrochemical destabilization of metallic soaps and possibly to electroosmotic transport.

  17. 49 CFR 192.279 - Copper pipe.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Transportation Other Regulations Relating to Transportation (Continued) PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) PIPELINE SAFETY TRANSPORTATION OF NATURAL AND OTHER GAS BY PIPELINE: MINIMUM FEDERAL SAFETY STANDARDS Joining of Materials Other Than by Welding § 192.279...

  18. 40 CFR 721.10688 - Copper, chloro[tris(2-chloroethyl) phosphite-.kappa.P]-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) phosphite-.kappa.P]-. 721.10688 Section 721.10688 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10688 Copper, chloro[tris(2-chloroethyl) phosphite-.kappa.P]-. (a... copper, chloro[tris(2-chloroethyl) phosphite-.kappa.P]- (PMN P-13-221; CAS No. 24484-01-3) is subject to...

  19. Mechanisms of copper homeostasis in bacteria

    PubMed Central

    Argüello, José M.; Raimunda, Daniel; Padilla-Benavides, Teresita

    2013-01-01

    Copper is an important micronutrient required as a redox co-factor in the catalytic centers of enzymes. However, free copper is a potential hazard because of its high chemical reactivity. Consequently, organisms exert a tight control on Cu+ transport (entry-exit) and traffic through different compartments, ensuring the homeostasis required for cuproprotein synthesis and prevention of toxic effects. Recent studies based on biochemical, bioinformatics, and metalloproteomics approaches, reveal a highly regulated system of transcriptional regulators, soluble chaperones, membrane transporters, and target cuproproteins distributed in the various bacterial compartments. As a result, new questions have emerged regarding the diversity and apparent redundancies of these components, their irregular presence in different organisms, functional interactions, and resulting system architectures. PMID:24205499

  20. The effects of copper on Na(+)/K (+)-ATPase and aquaporin expression in two euryhaline invertebrates.

    PubMed

    Boyle, R T; Oliveira, L F; Bianchini, A; Souza, M M

    2013-03-01

    We used immunocytochemical and fluorometric techniques to show that gill cells of two marine invertebrates, the crab Neohelice granulata (osmoregulator) and the clam Mesodesma mactroides (osmoconformer), increase the expression of membrane transporters [Na(+)/K(+)-ATPase and aquaporin (AQP1)] after whole-animals exposure (96 h) to sublethal concentrations of copper in water of salinity 30 ppt, when both clams and crabs are isosmotic with respect to the environmental medium. A plausible interpretation of our findings is that this increased expression in membrane transporters may serve as an attempt to ameliorate the deleterious effects of copper on the mechanisms involved in ion and volume regulation in gill cells.

  1. Peristaltic transport of copper-water nanofluid saturating porous medium

    NASA Astrophysics Data System (ADS)

    Abbasi, F. M.; Hayat, T.; Ahmad, B.

    2015-03-01

    Prime goal of present study is to model the problem for peristaltic transport of copper-water nanofluid in an asymmetric channel. The fluid fills porous space. Analysis is carried out in the presence of mixed conviction, viscous dissipation and heat generation/absorption. Long wavelength and low Reynolds number approximations are utilized in problem formulation. Numerical computations are presented for the axial velocity, pressure gradient, streamlines, temperature and heat transfer rate at the boundary. Graphical analysis is carried out to examine the effects of sundry parameters on flow quantities of interest. Results revealed that the axial velocity of copper-water nanofluid decreases with an increase in the nanoparticle volume fraction. Copper nanoparticles prove effective coolant since they sufficiently reduce the fluid temperature and show increase in the heat transfer between the fluid and solid boundary. Moreover temperature of the fluid decreases by increasing the permeability of porous medium.

  2. Slip Effects on Mixed Convective Peristaltic Transport of Copper-Water Nanofluid in an Inclined Channel

    PubMed Central

    Abbasi, Fahad Munir; Hayat, Tasawar; Ahmad, Bashir; Chen, Guo-Qian

    2014-01-01

    Peristaltic transport of copper-water nanofluid in an inclined channel is reported in the presence of mixed convection. Both velocity and thermal slip conditions are considered. Mathematical modelling has been carried out using the long wavelength and low Reynolds number approximations. Resulting coupled system of equations is solved numerically. Quantities of interest are analyzed through graphs. Numerical values of heat transfer rate at the wall for different parameters are obtained and examined. Results showed that addition of copper nanoparticles reduces the pressure gradient, axial velocity at the center of channel, trapping and temperature. Velocity slip parameter has a decreasing effect on the velocity near the center of channel. Temperature of nanofluid increases with increase in the Grashoff number and channel inclination angle. It is further concluded that the heat transfer rate at the wall increases considerably in the presence of copper nanoparticles. PMID:25170908

  3. Copper interstitial recombination centers in Cu 3 N

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

    Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam

    We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

  4. Copper interstitial recombination centers in Cu 3 N

    DOE PAGES

    Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; ...

    2018-06-04

    We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

  5. 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

  6. 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.

  7. Molecular Mediators Governing Iron-Copper Interactions

    PubMed Central

    Gulec, Sukru; Collins, James F.

    2015-01-01

    Given their similar physiochemical properties, it is a logical postulate that iron and copper metabolism are intertwined. Indeed, iron-copper interactions were first documented over a century ago, but the homeostatic effects of one on the other has not been elucidated at a molecular level to date. Recent experimental work has, however, begun to provide mechanistic insight into how copper influences iron metabolism. During iron deficiency, elevated copper levels are observed in the intestinal mucosa, liver, and blood. Copper accumulation and/or redistribution within enterocytes may influence iron transport, and high hepatic copper may enhance biosynthesis of a circulating ferroxidase, which potentiates iron release from stores. Moreover, emerging evidence has documented direct effects of copper on the expression and activity of the iron-regulatory hormone hepcidin. This review summarizes current experimental work in this field, with a focus on molecular aspects of iron-copper interplay and how these interactions relate to various disease states. PMID:24995690

  8. 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.

  9. Pathogenic adaptations to host-derived antibacterial copper

    PubMed Central

    Chaturvedi, Kaveri S.; Henderson, Jeffrey P.

    2014-01-01

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

  10. Geomorphology of the lower Copper River, Alaska

    USGS Publications Warehouse

    Brabets, T.P.

    1996-01-01

    The Copper River, located in southcentral Alaska, drains an area of more than 24,000 square miles. About 30 miles above its mouth, this large river enters Miles Lake, a proglacial lake formed by the retreat of Miles Glacier. Downstream from the outlet of Miles Lake, the Copper River flows past the face of Childs Glacier before it enters a large, broad, alluvial flood plain. The Copper River Highway traverses this flood plain and in 1996, 11 bridges were located along this section of the highway. These bridges cross parts or all of the Copper River and in recent years, some of these bridges have sustained serious damage due to the changing course of the Copper River. Although the annual mean discharge of the lower Copper River is 57,400 cubic feet per second, most of the flow occurs during the summer months from snowmelt, rainfall, and glacial melt. Approximately every six years, an outburst flood from Van Cleve Lake, a glacier-dammed lake formed by Miles Glacier, releases approximately 1 million acre-feet of water into the Copper River. At the peak outflow rate from Van Cleve Lake, the flow of the Copper River will increase an additional 140,000 and 190,000 cubic feet per second. Bedload sampling and continuous seismic reflection were used to show that Miles Lake traps virtually all the bedload being transported by the Copper River as it enters the lake from the north. The reservoir-like effect of Miles Lake results in the armoring of the channel of the Copper River downstream from Miles Lakes, past Childs Glacier, until it reaches the alluvial flood plain. At this point, bedload transport begins again. The lower Copper River transports 69 million tons per year of suspended sediment, approximately the same quantity as the Yukon River, which drains an area of more than 300,000 square miles. By correlating concurrent flows from a long-term streamflow- gaging station on the Copper River with a short-term streamflow-gaging station at the outlet of Miles Lake, long-term flow characteristics of the lower Copper River were synthesized. Historical discharge and cross-section data indicate that as late as 1970, most of the flow of the lower Copper River was through the first three bridges of the Copper River Highway as it begins to traverse the alluvial flood plain. In the mid 1980's, a percentage of the flow had shifted away from these three bridges and in 1995, only 51 percent of the flow of the Copper River passed through them. Eight different years of aerial photography of the lower Copper River were analyzed using Geographical Information System techniques. This analysis indicated that no major channel changes were caused by the 1964 earthquake. A flood in 1981 that had a recurrence interval of more than 100 years caused significant channel changes in the lower Copper River. A probability analysis of the lower Copper River indicated stable areas and the long-term locations of channels. By knowing the number of times a particular area has been occupied by water and the last year an area was occupied by water, areas of instability can be located. A Markov analysis of the lower Copper River indicated that the tendency of the flood plain is to remain in its current state. Large floods of the magnitude of the 1981 event are believed to be the cause of major changes in the lower Copper River.

  11. Geomorphology of the lower Copper River, Alaska

    USGS Publications Warehouse

    Brabets, Timothy P.

    1997-01-01

    The Copper River, located in southcentral Alaska, drains an area of more than 24,000 square miles. About 30 miles above its mouth, this large river enters Miles Lake, a proglacial lake formed by the retreat of Miles Glacier. Downstream from the outlet of Miles Lake, the Copper River flows past the face of Childs Glacier before it enters a large, broad, alluvial flood plain. The Copper River Highway traverses this flood plain and in 1995, 11 bridges were located along this section of the highway. These bridges cross parts of the Copper River and in recent years, some of these bridges have sustained serious damage due to the changing course of the Copper River. Although the annual mean discharge of the lower Copper River is 57,400 cubic feet per second, most of the flow occurs during the summer months from snowmelt, rainfall, and glacial melt. Approximately every six years, an outburst flood from Van Cleve Lake, a glacier-dammed lake formed by Miles Glacier, releases approximately 1 million acre-feet of water into the Copper River. When the outflow rate from Van Cleve Lake reaches it peak, the flow of the Copper River will increase between 150,000 to 190,000 cubic feet per second. Data collected by bedload sampling and continuous seismic reflection indicated that Miles Lake traps virtually all the bedload being transported by the Copper River as it enters the lake from the north. The reservoir-like effect of Miles Lake results in the armoring of the channel of the Copper River downstream from Miles Lake, past Childs Glacier, until it reaches the alluvial flood plain. At this point, bedload transport begins again. The lower Copper River transports 69 million tons per year of suspended sediment, approximately the same quantity as the Yukon River, which drains an area of more than 300,000 square miles. By correlating concurrent flows from a long-term streamflow-gaging station on the Copper River with a short-term streamflow-gaging station at the outlet of Miles Lake, long-term flow characteristics of the lower Copper River were synthesized. Historical discharge and cross-section data indicate that as late as 1970, most of the flow of the lower Copper River was through the first three bridges of the Copper River Highway as it begins to traverse the alluvial flood plain. In the mid 1980's, a percentage of the flow had shifted away from these three bridges and in 1995, only 51 percent of the flow of the Copper River passed through them. Eight different years of aerial photography of the lower Copper River were analyzed using Geographical Information System techniques. This analysis indicated that no major channel changes were caused by the 1964 earthquake. However, a flood in 1981 that had a recurrence interval of more than 100 years caused significant channel changes in the lower Copper River. A probability analysis of the lower Copper River indicated stable areas and the long-term locations of channels. By knowing the number of times a particular area has been occupied by water and the last year an area was occupied by water, areas of instability can be located. A Markov analysis of the lower Copper River indicated that the tendency of the flood plain is to remain in its current state. Large floods of the magnitude of the 1981 event are believed to be the cause of major changes in the lower Copper River.

  12. Electro deposition of cuprous oxide for thin film solar cell applications

    NASA Astrophysics Data System (ADS)

    Shahrestani, Seyed Mohammad

    p and n type copper oxide semiconductor layers were fabricated by electrochemistry using new approaches for photovoltaic applications. Thin films were electroplated by cathodic polarization on a copper foil or indium tin oxide (ITO) substrates. The optimum deposition conditions (composition, pH and temperature of the electrolyte and applied potential) of the layers as thin films have been identified; in particular the conditions that allow getting the n-type layers have been well identified for the first time. The configuration of a photo - electrochemical cell was used to characterize the spectral response of the layers. It was shown that the p type layers exhibit a photocurrent in the cathode potential region and n layers exhibit photo current in the anode potential region. Measurements of electrical resistivity of electro chemically deposited layers of p and n type Cu2O, showed that the resistivity of p-type Cu2O varies from 3.2 x 105 to 2.0 x 108 Ocm. These values depend the electrodepositing conditions such as the pH of the solution, the deposition potential and temperature. The influence of several plating parameters of the p type layers of Cu2O, such as applied potential, pH and temperature of the bath on the chemical composition, degree of crystallinity, grain size and orientation parameters of the sample was systematically studied using X-ray diffraction and scanning electron microscopy. Depending of the electro-deposition potential, two different surface morphologies with various preferential crystal orientations were obtained for the temperatures of the electro-deposition of 30 °C and pH 9. For the same temperature, the layers of p type Cu2O of highly crystalline p type are obtained at pH 12, indicating that the crystallinity depends on the pH of the bath. Also, it has been shown that the morphology of Cu2O layers was changed by varying the potential and the duration of deposition, as well as the temperature of the solution. The conditions for the electro-deposition of Cu2O n-type were identified consistently for the first time. The electro-deposition electrolyte is based 0.01M acetate copper and 0.1 M sodium acetate: it has a pH between 6.3 and 4, a potential of from 0 to -0.25 V vs. Ag / AgCl and a temperature of 60oC. The optimum annealing temperature of the n-type Cu2O layers is between 120-150oC for the annealing time of 30 to 120 minutes. Resistivity of the n-type films varies between 5 x 103 and 5 x 104 at pH 4 to pH 6.4. We have shown for the first time that bubbling nitrogen gas in the electroplating cell improves significantly the spectral response of the electro-deposited n-type thin film. A two steps electro-deposition process was implemented to make the p-n homojunction cuprous oxide. Indium tin oxide (ITO) was used as a transparent conductive oxide substrate. A p-Cu2O was electrodeposited on ITO. After heat treatment a thin film layer of n-Cu 2O was electrodeposited on top of previous layer. The performance of a p-n homojunction photovoltaic solar cell of Cu2O was determined. The short-circuit current and the open circuit voltage were respectively determined to be as 0.35 volts and 235 muA/cm2. The fill factor (FF) and conversion efficiency of light into electricity were respectively measured to be 0.305 and 0.082%.

  13. Sublethal effects of copper sulphate compared to copper nanoparticles in rainbow trout (Oncorhynchus mykiss) at low pH: physiology and metal accumulation.

    PubMed

    Al-Bairuty, Genan A; Boyle, David; Henry, Theodore B; Handy, Richard D

    2016-05-01

    A few studies have investigated the interaction between copper toxicity and water pH in fishes, but little is known about the effects of acidic pH on the toxicity of copper nanoparticles (Cu-NPs). This study aimed to describe the sub-lethal toxic effects of Cu-NPs compared to CuSO4 at neutral and acidic water pH values in juvenile rainbow trout. Fish were exposed in triplicate (3 tanks/treatment) to control (no added Cu), or 20μgl(-1) of either Cu as CuSO4 or Cu-NPs, at pH 7 and 5 in a semi-static aqueous exposure regime for up to 7 days. Acidification of the water altered the mean primary particle size (at pH 7, 60±2nm and pH 5, 55±1nm) and dialysis experiments to measure dissolution showed an increased release of dissolved Cu from Cu-NPs at pH 5 compared to pH 7. Copper accumulation was observed in the gills of trout exposed to CuSO4 and Cu-NPs at pH 7 and 5, with a greater accumulation from the CuSO4 treatment than Cu-NPs at each pH. The liver also showed Cu accumulation with both Cu treatments at pH 7 only, whereas, the spleen and kidney did not show measurable accumulation of Cu at any of the water pH values. Exposure to acid water caused changes in the ionoregulatory physiology of control fish and also altered the observed effects of Cu exposure; at pH 5, branchial Na(+)/K(+)-ATPase activity was greater than at pH 7 and the inhibition of Na(+)/K(+)-ATPase activity caused by exposure to CuSO4 at pH 7 was also not observed. There were some changes in haematology and depletion of plasma Na(+) at pH 7 and 5 due to Cu exposure, but there were few material-type or pH effects. Overall, the data show that the accumulation of Cu is greater from CuSO4 than Cu-NPs; however, understanding of the effects of low pH on bioavailability of CuSO4 may not be directly transferred to Cu-NPs without further consideration of the physico-chemical behaviour of Cu-NPs in acid water. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Hierarchical and Well-Ordered Porous Copper for Liquid Transport Properties Control.

    PubMed

    Pham, Quang N; Shao, Bowen; Kim, Yongsung; Won, Yoonjin

    2018-05-09

    Liquid delivery through interconnected pore network is essential for various interfacial transport applications ranging from energy storage to evaporative cooling. The liquid transport performance in porous media can be significantly improved through the use of hierarchical morphology that leverages transport phenomena at different length scales. Traditional surface engineering techniques using chemical or thermal reactions often show nonuniform surface nanostructuring within three-dimensional pore network due to uncontrollable diffusion and reactivity in geometrically complex porous structures. Here, we demonstrate hierarchical architectures on the basis of crystalline copper inverse opals using an electrochemistry approach, which offers volumetric controllability of structural and surface properties within the complex porous metal. The electrochemical process sequentially combines subtractive and additive steps-electrochemical polishing and electrochemical oxidation-to improve surface wetting properties without sacrificing structural permeability. We report the transport performance of the hierarchical inverse opals by measuring the capillary-driven liquid rise. The capillary performance parameter of hierarchically engineered inverse opal ( K/ R eff = ∼5 × 10 -3 μm) is shown to be higher than that of a typical crystalline inverse opal ( K/ R eff = ∼1 × 10 -3 μm) owing to the enhancement in fluid permeable and hydrophilic pathways. The new surface engineering method presented in this work provides a rational approach in designing hierarchical porous copper for transport performance enhancements.

  15. Effects of three types of trace element supplementation on the fertility of three commercial dairy herds.

    PubMed

    Black, D H; French, N P

    2004-05-22

    The effects on the fertility of three commercial dairy herds of three types of copper- and selenium-containing mineral supplements was investigated. As the cows on each farm were dried off they were allocated to one of three treatment groups, and treated with either subcutaneous injections of copper and selenium, or two matrix intraruminal trace element boluses, or two glass intraruminal trace element boluses. When the data from the 406 cows on the three farms were combined, there was a significant difference between the conception rates of the three groups (P < 0.001). The cows treated with the glass boluses conceived at a rate 1.8 times greater than those treated by injection (P < 0.001), and at a rate 1.5 times greater than those treated with matrix boluses (P = 0.002). These differences were associated with a significantly higher likelihood of service resulting in a conception in the group treated with glass boluses than in the group treated by injection (P = 0.004). After adjusting for time from calving, time from treatment, time of year and farm, there was a significant (P = 0.012) difference in glutathione peroxidase activities between the treatments, with the group treated by injection having a significantly lower activity than the groups treated with boluses.

  16. The effects of coadministration of dietary copper and zinc supplements on atherosclerosis, antioxidant enzymes and indices of lipid peroxidation in the cholesterol-fed rabbit

    PubMed Central

    Alissa, Eman M; Bahijri, Suhad M; Lamb, David J; Ferns, Gordon A A

    2004-01-01

    It has previously been shown that dietary copper can modulate the extent of atherosclerosis in the thoracic aorta of cholesterol-fed rabbits. The metabolism of copper and zinc are closely related, and it has been hypothesized that the balance of dietary copper to zinc may be important in determining coronary risk. Hence, we have investigated the interaction between dietary copper and zinc in atherogenesis in the New Zealand White rabbit. Juvenile male rabbits were randomly allocated to eight groups. Four groups were fed a normal chow diet with zinc (0.5%, w/w), copper (0.2%, w/w), copper plus zinc or neither in their drinking water for 12 weeks. Four other groups were fed a diet containing 0.25–1% (w/w) cholesterol plus zinc, copper, both or neither. Serum cholesterol of individual animals was maintained at approximately 20 mmol/l. Integrated plasma cholesterol levels were similar for all groups receiving cholesterol and significantly higher than those in the chow-fed groups (P < 0.001). Aortic copper concentrations were higher in the animals receiving cholesterol diets with copper compared to rabbits receiving normal chow and copper (P < 0.001). Aortic zinc content was significantly higher in cholesterol-fed rabbits supplemented with zinc alone or with copper than in those fed cholesterol alone (P < 0.001). Plasma ceruloplasmin concentrations were significantly higher in groups receiving cholesterol, irrespective of their trace element supplementation (P < 0.001). However, trace element supplementation increased the level significantly (P < 0.05). Trace element supplements did not appear to affect erythrocyte superoxide dismutase in the cholesterol-fed animals; however, zinc supplementation was associated with a significant increase in the enzyme in chow-fed animals (P < 0.05). The activity of the enzyme per mg of protein in aortic tissue was higher in animals receiving copper in the presence of cholesterol (P < 0.05) but not significantly so in its absence. Dietary trace element supplementation in cholesterol-fed animals was associated with a significant reduction in aortic lesion area. Plasma thiobarbituric acid-reactive substances and FOX concentrations were both significantly higher in the cholesterol-fed rabbits compared with the animals that fed on a chow diet (P < 0.001), and these were reduced significantly by dietary copper or zinc supplementation (P < 0.001). Hence, dietary supplements of copper or zinc at the doses used both inhibited aortic atherogenesis in the cholesterol-fed rabbits, although there was no significant additional effect when given in combination. PMID:15379959

  17. Effects of a copper-tolerant grass (Agrostis capillaris) on the ecosystem of a copper-contaminated arable soil

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

    Boon, G.T.; Bouwman, L.A.; Bloem, J.

    1998-10-01

    To test how a dysfunctioning ecosystem of a severely metal-polluted soil responds to renewed plant growth, a pot experiment was conducted with soil from an experimental arable field with pH and copper gradients imposed 13 years ago. In this experiment, four pH/copper combinations from this field were either planted with a pH- and copper-resistant grass cultivar or remained fallow. During a 10-week period, the dynamics of the microbial activity and of the abundances of bacteria, protozoa. and nematodes were measured, as were the dynamics of several chemical soil parameters. After 13 years of copper, which had resulted in severely reducedmore » crop growth, no effects were observed on bacterial numbers, respiration, or protozoan numbers, but bacterial growth was strongly reduced in the low pH plots, and even more so in low pH plots enriched with copper. Of the organisms, only nematodes were negatively affected under conditions of high copper load at low pH. In these plots, numbers belonging to all feeding categories were strongly reduced. Planting of a copper-tolerant grass variety, Agrostis capillaris L. var. Parys Mountain, resulted within 10 weeks in faster bacterial growth and more protozoa and bacterivorous nematodes in comparison with fallow controls; these effects were markedly strongest in the acidic, copper-enriched soils. During incubation, fungivorous nematodes increased in all treatments, in fallow and in planted pots and in the pots with high-copper, low-pH soil. The results of this experiment suggest that introduction of plant growth is one of the major causes of increased biological activity in acidic contaminated soils. Planting such soils with metal-tolerant plant species can reestablish the necessary food base to support soil organism growth, and this can lead to numerous positive effects, reversing the loss of soil functions due to the high copper levels under acidic conditions.« less

  18. Replacement of a cytosolic copper/zinc superoxide dismutase by a novel cytosolic manganese superoxide dismutase in crustaceans that use copper (haemocyanin) for oxygen transport.

    PubMed Central

    Brouwer, Marius; Hoexum Brouwer, Thea; Grater, Walter; Brown-Peterson, Nancy

    2003-01-01

    The blue crab, Callinectes sapidus, which uses the copper-dependent protein haemocyanin for oxygen transport, lacks the ubiquitous cytosolic copper-dependent enzyme copper/zinc superoxide dismutase (Cu,ZnSOD) as evidenced by undetectable levels of Cu,ZnSOD activity, protein and mRNA in the hepatopancreas (the site of haemocyanin synthesis) and gills. Instead, the crab has an unusual cytosolic manganese SOD (cytMnSOD), which is retained in the cytosol, because it lacks a mitochondrial transit peptide. A second familiar MnSOD is present in the mitochondria (mtMnSOD). This unique phenomenon occurs in all Crustacea that use haemocyanin for oxygen transport. Molecular phylogeny analysis suggests the MnSOD gene duplication is as old as the origin of the arthropod phylum. cytMnSOD activity in the hepatopancreas changes during the moulting cycle of the crab. Activity is high in intermoult crabs and non-detectable in postmoult papershell crabs. mtMnSOD is present in all stages of the moulting cycle. Despite the lack of cytCu,ZnSOD, crabs have an extracellular Cu,ZnSOD (ecCu,ZnSOD) that is produced by haemocytes, and is part of a large, approx. 160 kDa, covalently-linked protein complex. ecCu,ZnSOD is absent from the hepatopancreas of intermoult crabs, but appears in this tissue at premoult. However, no ecCu,ZnSOD mRNA can be detected, suggesting that the protein is recruited from the haemolymph. Screening of different taxa of the arthropod phylum for Cu,ZnSOD activity shows that those crustaceans that use haemoglobin for oxygen transport have retained cytCu,ZnSOD. It appears, therefore, that the replacement of cytCu,ZnSOD with cytMnSOD is part of an adaptive response to the dynamic, haemocyanin-linked, fluctuations in copper metabolism that occur during the moulting cycle of the crab. PMID:12769817

  19. Salivary levels of nickel, chromium, iron, and copper in patients treated with metal or esthetic fixed orthodontic appliances: A retrospective cohort study.

    PubMed

    Lages, Renata Bandeira; Bridi, Enrico Coser; Pérez, Carlos Alberto; Basting, Roberta Tarkany

    2017-03-01

    The purpose of this retrospective cohort study was to measure the salivary levels of nickel (Ni), chromium (Cr), iron (Fe) and copper (Cu) released from metal and esthetic fixed orthodontic appliances. Ninety patients were divided into three groups (n=30): control (those who had never undergone orthodontic treatment), metal appliance (stainless steel brackets and bands, and nitinol archwires) and esthetic appliance (polycarbonate brackets and tubes, and rhodium-coated nitinol archwires). Patients undergoing orthodontic treatment had used their appliances for periods between one and six months. Ni, Cr, Fe and Cu salivary concentrations were measured by the Total Reflection X-Ray Fluorescence technique. Kruskal-Wallis and Bonferroni-Dunn test showed that Ni (p=0.027) and Cr (p=0.040) concentrations were significantly higher for patients undergoing metallic orthodontic treatment than for the esthetic group. No significant difference regarding Ni and Cr (p=0.447) concentrations were observed between the metal and the control groups (p=0.464 and p=0.447, respectively) or between the esthetic and the control groups (p=0.698 and p=0.912, respectively). Ni and Cr concentrations were significantly influenced by the type of appliance used. Fe and Cu concentrations were not affected by the type or use of orthodontic appliances. Copyright © 2016 Elsevier GmbH. All rights reserved.

  20. Questa baseline and pre-mining ground-water quality investigation. 12. Geochemical and reactive-transport modeling based on tracer injection-synoptic sampling studies for the Red River, New Mexico, 2001-2002

    USGS Publications Warehouse

    Ball, James W.; Runkel, Robert L.; Nordstrom, D. Kirk

    2005-01-01

    Reactive-transport processes in the Red River, downstream from the town of Red River in north-central New Mexico, were simulated using the OTEQ reactive-transport model. The simulations were calibrated using physical and chemical data from synoptic studies conducted during low-flow conditions in August 2001 and during March/April 2002. Discharge over the 20-km reach from the town of Red River to the USGS streamflow-gaging station near the town of Questa ranged from 395 to 1,180 L/s during the 2001 tracer and from 234 to 421 L/s during the 2002 tracer. The pH of the Red River ranged from 7.4 to 8.5 during the 2001 tracer and from 7.1 to 8.7 during the 2002 tracer, and seep and tributary samples had pH values of 2.8 to 9.0 during the 2001 tracer and 3.8 to 7.2 during the 2002 tracer. Mass-loading calculations allowed identification of several specific locations where elevated concentrations of potential contaminants entered the Red River . These locations, characterized by features on the north side of the Red River that are known to be sources of low-pH water containing elevated metal and sulfate concentrations, are: the initial 2.4 km of the study reach, including Bitter Creek, the stream section from 6.2 to 7.8 km, encompassing La Bobita well and the Hansen debris fan, Sulphur Gulch, at about 10.5 km, the area near Portal Springs, from 12.2 to 12.6 km, and the largest contributors of mass loading, the 13.7 to 13.9 km stream section near Cabin Springs and the 14.7 to 17.5 km stream section from Shaft Spring to Thunder Bridge, Goathill Gulch, and Capulin Canyon. Speciation and saturation index calculations indicated that although solubility limits the concentration of aluminum above pH 5.0, at pH values above 7 and aluminum concentrations below 0.3 mg/L inorganic speciation and mineral solubility controls no longer dominate and aluminum-organic complexing may occur. The August 2001 reactive-transport simulations included dissolved iron(II) oxidation, constrained using measured concentrations of dissolved iron(II) and dissolved iron(total). Both simulations included precipitation of amorphous Al(OH)3 and hydrous ferric oxide as Fe(OH)3, and sorption of copper and zinc to the precipitated hydrous ferric oxide. Simulations revealed that hydrogen, iron, aluminum, copper, and zinc were non-conservative and that mineral precipitation can account for iron and aluminum concentrations. Copper and zinc concentrations can be accounted for by simulating their sorption to hydrous ferric oxide forming in the water column of the Red River , although hydrous manganese oxides also may be important sorption substrates.

  1. Detachment of sprayed colloidal copper oxychloride-metalaxyl fungicides by a shallow water flow.

    PubMed

    Pose-Juan, Eva; Paradelo-Pérez, Marcos; Rial-Otero, Raquel; Simal-Gándara, Jesus; López-Periago, José E

    2009-06-01

    Flow shear stress induced by rainfall promotes the loss of the pesticides sprayed on crops. Some of the factors influencing the losses of colloidal-size particulate fungicides are quantified by using a rotating shear system model. With this device it was possible to analyse the flow shear influencing washoff of a commercial fungicide formulation based on a copper oxychloride-metalaxyl mixture that was sprayed on a polypropylene surface. A factor plan with four variables, i.e. water speed and volume (both variables determining flow boundary stress in the shear device), formulation dosage and drying temperature, was set up to monitor colloid detachment. This experimental design, together with sorption experiments of metalaxyl on copper oxychloride, and the study of the dynamics of metalaxyl and copper oxychloride washoff, made it possible to prove that metalaxyl washoff from a polypropylene surface is controlled by transport in solution, whereas that of copper oxychloride occurs by particle detachment and transport of particles. Average losses for metalaxyl and copper oxychloride were, respectively, 29 and 50% of the quantity applied at the usual recommended dosage for crops. The key factors affecting losses were flow shear and the applied dosage. Empirical models using these factors provided good estimates of the percentage of fungicide loss. From the factor analysis, the main mechanism for metalaxyl loss induced by a shallow water flow is solubilisation, whereas copper loss is controlled by erosion of copper oxychloride particles.

  2. Growth and Characterization of the p-type Semiconductors Tin Sulfide and Bismuth Copper Oxy Selenide

    NASA Astrophysics Data System (ADS)

    Francis, Jason

    BiCuOSe and SnS are layered, moderate band gap (epsilon G ≈ 1 eV) semiconductors that exhibit intrinsic p type conductivity. Doping of BiCuOSe with Ca results in a slight expansion of the lattice and an increase of the hole concentration from 10 18 cm--3 to greater than 1020 cm --3. The large carrier density in undoped films is the result of copper vacancies. Mobility is unaffected by doping, remaining constant at 1.5 cm2V--1s--1 in both undoped and doped films, because the Bi-O layers serve as the source of carriers, while transport occurs within the Cu-Se layers. Bi possesses a 6s2 lone pair that was expected to hybridize with the oxygen p states at the top of the valence band, resulting in high hole mobility as compared to similar materials such as LaCuOSe, which lack this lone pair. However, both LaCuOSe and BiCuOSe have similar hole mobility. X-ray absorption and emission spectroscopy, combined with density functional theory calculations, reveal that the Bi 6 s states contribute deep within the valence band, forming bonding and anti-bonding states with O 2p at 11 eV and 3 eV below the valence band maximum, respectively. Hence, the Bi lone pair does not contribute at the top of the valence band and does not enhance the hole mobility. The Bi 6p states contribute at the bottom of the conduction band, resulting in a smaller band gap for BiCuOSe than LaCuOSe (1 eV vs. 3 eV). SnS is a potential photovoltaic absorber composed of weakly coupled layers stacked along the long axis. This weak coupling results in the formation of strongly oriented films on amorphous substrates. The optical band gap is 1.2 eV, in agreement with GW calculations. Absorption reaches 105 cm--1 within 0.5 eV of the band gap. The p type conduction arises from energetically favorable tin vacancies. Variation of growth conditions yields carrier densities of 1014 -- 1016 cm--3 and hole mobility of 7 -- 15 cm2V--1s--1. SnS was alloyed with rocksalt CaS, which was predicted to form a rocksalt structure when the calcium content is increased past 18%. Films of Sn1--x CaxS with x from 0.4 to 0.9 adopt the rocksalt structure with a band gap of 1.1-1.3 eV, with absorption greater than 105 cm--1 within about 0.7 eV of the band gap. The lattice contracts as the calcium content of the films is increased, reaching 5.7 A when x = 0.93. Films are highly insulating, but Seebeck measurements do indicate p type conduction.

  3. Understanding and Control of Bipolar Self-Doping in Copper Nitride

    PubMed Central

    Fioretti, Angela N.; Schwartz, Craig P.; Vinson, John; Nordlund, Dennis; Prendergast, David; Tamboli, Adele C.; Caskey, Christopher M.; Tuomisto, Filip; Linez, Florence; Christensen, Steven T.; Toberer, Eric S.; Lany, Stephan; Zakutayev, Andriy

    2016-01-01

    Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu3N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu3N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu3N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu3N with an electron density of 1017 cm−3 for low growth temperature (≈ 35 °C) and p-type with a hole density between 1015 cm−3 and 1016 cm−3 for elevated growth temperatures (50 °C to 120 °C). Mobility for both types of Cu3N was ≈ 0.1 cm2/Vs to 1 cm2/V. Additionally, temperature-dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that VCu defects form preferentially in p-type Cu3N while Cui defects form preferentially in n-type Cu3N; suggesting that Cu3N is a compensated semiconductor with conductivity type resulting from a balance between donor and acceptor defects. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu3N, that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials, and provide a framework that can be applied when considering the properties of such materials in general. PMID:27746508

  4. Understanding and Control of Bipolar Self-Doping in Copper Nitride

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

    Fioretti, Angela N.; Schwartz, Craig P.; Vinson, John

    2016-05-14

    Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu3N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu3N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu3N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu3N with 1017 electrons/cm3 for low growth temperature (approximately 35more » degrees C) and p-type with 1015 holes/cm3-1016 holes/cm3 for elevated growth temperatures (50 degrees C-120 degrees C). Mobility for both types of Cu3N was approximately 0.1 cm2/Vs-1 cm2/Vs. Additionally, temperature-dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that VCu defects form preferentially in p-type Cu3N, while Cui defects form preferentially in n-type Cu3N, suggesting that Cu3N is a compensated semiconductor with conductivity type resulting from a balance between donor and acceptor defects. Based on these theoretical and experimental results, we propose a kinetic defectformation mechanism for bipolar doping in Cu3N that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials and provide a framework that can be applied when considering the properties of such materials in general.« less

  5. Copper stabilization via spinel formation during the sintering of simulated copper-laden sludge with aluminum-rich ceramic precursors.

    PubMed

    Tang, Yuanyuan; Chui, Stephen Sin-Yin; Shih, Kaimin; Zhang, Lingru

    2011-04-15

    The feasibility of incorporating copper-laden sludge into low-cost ceramic products, such as construction ceramics, was investigated by sintering simulated copper-laden sludge with four aluminum-rich ceramic precursors. The results indicated that all of these precursors (γ-Al(2)O(3), corundum, kaolinite, mullite) could crystallochemically stabilize the hazardous copper in the more durable copper aluminate spinel (CuAl(2)O(4)) structure. To simulate the process of copper transformation into a spinel structure, CuO was mixed with the four aluminum-rich precursors, and fired at 650-1150 °C for 3 h. The products were examined using powder X-ray diffraction (XRD) and scanning electron microscopic techniques. The efficiency of copper transformation among crystalline phases was quantitatively determined through Rietveld refinement analysis of the XRD data. The sintering experiment revealed that the optimal sintering temperature for CuAl(2)O(4) formation was around 1000 °C and that the efficiency of copper incorporation into the crystalline CuAl(2)O(4) structure after 3 h of sintering ranged from 40 to 95%, depending on the type of aluminum precursor used. Prolonged leaching tests were carried out by using acetic acid with an initial pH value of 2.9 to leach CuO and CuAl(2)O(4) samples for 22 d. The sample leachability analysis revealed that the CuAl(2)O(4) spinel structure was more superior to stabilize copper, and suggested a promising and reliable technique for incorporating copper-laden sludge or its incineration ash into usable ceramic products. Such results also demonstrated the potential of a waste-to-resource strategy by using waste materials as part of the raw materials with the attainable temperature range used in the production of ceramics.

  6. Quantification of metal loads by tracer injection and synoptic sampling in Daisy Creek and the Stillwater River, Park County, Montana, August 1999

    USGS Publications Warehouse

    Nimick, David A.; Cleasby, Thomas E.

    2001-01-01

    A metal-loading study using tracer-injection and synoptic-sampling methods was conducted in Daisy Creek and a short reach of the Stillwater River during baseflow in August 1999 to quantify the metal inputs from acid rock drainage in the New World Mining District near Yellowstone National Park and to examine the downstream transport of these metals into the Stillwater River. Loads were calculated for many mainstem and inflow sites by combining streamflow determined using the tracer-injection method with concentrations of major ions and metals that were determined in synoptic water-quality samples. Water quality and aquatic habitat in Daisy Creek have been affected adversely by drainage derived from waste rock and adit discharge at the McLaren Mine as well as from natural weathering of pyrite-rich mineralized rock that comprises and surrounds the ore zones. However, the specific sources and transport pathways are not well understood. Knowledge of the main sources and transport pathways of metals and acid can aid resource managers in planning and conducting effective and cost-efficient remediation activities. The metals cadmium, copper, lead, and zinc occur at concentrations that are sufficiently elevated to be potentially lethal to aquatic life in Daisy Creek and to pose a toxicity risk in part of the Stillwater River. Copper is of most concern in Daisy Creek because it occurs at higher concentrations than the other metals. Acidic surface inflows had dissolved concentrations as high as 20.6 micrograms per liter (?g/L) cadmium, 26,900 ?g/L copper, 76.4 ?g/L lead, and 3,000 ?g/L zinc. These inflows resulted in maximum dissolved concentrations in Daisy Creek of 5.8 ?g/L cadmium, 5,790 ?g/L copper, 3.8 ?g/L lead, and 848 ?g/L zinc. Significant copper loading to Daisy Creek occurred only in the upper half of the stream. Sources included subsurface inflow and right-bank (mined side) surface inflows. Copper loads in left-bank (unmined side) surface inflows were negligible. Most (71 percent) of the total copper loading in the study reach occurred along a 341-foot reach near the stream?s headwaters. About 53 percent of the total copper load was contributed by five surface inflows that drain a manganese bog and the southern part of the McLaren Mine. Copper loading from subsurface inflow was substantial, contributing 46 percent of the total dissolved copper load to Daisy Creek. More than half of this subsurface copper loading occurred downstream from the reaches that received significant surface loading. Flow through the shallow subsurface appears to be the main copper-transport pathway from the McLaren Mine and surrounding altered and mineralized bedrock to Daisy Creek during base-flow conditions. Little is known about the source of acid and copper in this subsurface flow. However, possible sources include the mineralized rocks of Fisher Mountain upgradient of the McLaren Mine area, the surficial waste rock at the mine, and the underlying pyritic bedrock.

  7. Cyanide and Copper Recovery from Barren Solution of the Merrill Crowe Process

    NASA Astrophysics Data System (ADS)

    Parga, José R.; Valenzuela, Jesús L.; Díaz, J. A.

    This paper is a brief overview of the role of inducing the nucleated precipitation of copper and cyanide in a flashtube serpentine reactor, using sodium sulfide as the precipitate and sulfuric acid as pH control. The results showed that pH had a great effect on copper cyanide removal efficiency and the optimum pH was about 3 to 3.5. At this pH value copper cyanide removal efficiency could be achieved above 97 and 99 %, when influent copper concentration ions were 650 and 900 ppm respectively. In this process the cyanide associated with the copper, zinc, iron cyanide complexes are released as HCN gas under strong acidic conditions, allowing it to be recycled back to the cyanidation process as free cyanide.

  8. Quantifying the Performance of P-Type Transparent Conducting Oxides by Experimental Methods

    PubMed Central

    Fleischer, Karsten; Norton, Emma; Mullarkey, Daragh; Caffrey, David; Shvets, Igor V.

    2017-01-01

    Screening for potential new materials with experimental and theoretical methods has led to the discovery of many promising candidate materials for p-type transparent conducting oxides. It is difficult to reliably assess a good p-type transparent conducting oxide (TCO) from limited information available at an early experimental stage. In this paper we discuss the influence of sample thickness on simple transmission measurements and how the sample thickness can skew the commonly used figure of merit of TCOs and their estimated band gap. We discuss this using copper-deficient CuCrO2 as an example, as it was already shown to be a good p-type TCO grown at low temperatures. We outline a modified figure of merit reducing thickness-dependent errors, as well as how modern ab initio screening methods can be used to augment experimental methods to assess new materials for potential applications as p-type TCOs, p-channel transparent thin film transistors, and selective contacts in solar cells. PMID:28862695

  9. 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.

  10. Unexpected Role of the Copper Transporter ATP7A in PDGF-Induced Vascular Smooth Muscle Cell Migration

    PubMed Central

    Ashino, Takashi; Sudhahar, Varadarajan; Urao, Norifumi; Oshikawa, Jin; Chen, Gin-Fu; Wang, Huan; Huo, Yuqing; Finney, Lydia; Vogt, Stefan; McKinney, Ronald D.; Maryon, Edward B.; Kaplan, Jack H.; Ushio-Fukai, Masuko; Fukai, Tohru

    2010-01-01

    Rationale Copper, an essential nutrient, has been implicated in vascular remodeling and atherosclerosis with unknown mechanism. Bioavailability of intracellular copper is regulated not only by the copper importer CTR1, but also by the copper exporter ATP7A (Menke ATPase) whose function is achieved through copper-dependent translocation from trans-Golgi network (TGN). Platelet-derived growth factor (PDGF) promotes vascular smooth muscle cell (VSMC) migration, a key component of neointimal formation. Objective To determine the role of copper transporter ATP7A in PDGF-induced VSMC migration. Methods and Results Depletion of ATP7A inhibited VSMC migration in response to PDGF or wound scratch in a CTR1/copper-dependent manner. PDGF stimulation promoted ATP7A translocation from the TGN to lipid rafts which localized at the leading edge, where it colocalized with PDGF receptor and Rac1, in migrating VSMCs. Mechanistically, ATP7A siRNA or CTR siRNA prevented PDGF-induced Rac1 translocation to the leading edge, thereby inhibiting lamellipodia formation. In addition, ATP7A depletion prevented a PDGF-induced decrease in copper level and secretory copper enzyme precursor pro-lysyl oxidase (Pro-LOX) in lipid raft fraction as well as PDGF-induced increase in LOX activity. In vivo, ATP7A expression was markedly increased and copper accumulation was observed by synchrotron-based X-ray fluorescence microscopy at neointimal VSMCs in wire injury model. Conclusions These findings suggest that ATP7A plays an important role in copper-dependent PDGF-stimulated VSMC migration via recruiting Rac1 to lipid rafts at the leading edge as well as regulating LOX activity. This may contribute to neointimal formation after vascular injury. Our findings provide insight into ATP7A as a novel therapeutic target for vascular remodeling and atherosclerosis. PMID:20671235

  11. Synthesis and structural characterization of polyoxometalates incorporating with anilinium cations and facile preparation of hybrid film

    NASA Astrophysics Data System (ADS)

    Fukaya, Keisuke; Srifa, Atthapon; Isikawa, Eri; Naruke, Haruo

    2010-08-01

    The self-assembly reaction of tungstate and copper(II) in the presence of aniline (ANI) and phosphoric acid led to the formation of an anilinium (ANIH +) salt of mono-substituted Keggin-type polyoxotungstophosphate (ANIH) 5[PCu(H 2O)W 11O 39](ANI)·8H 2O ( 1), while the reaction of heptamolybdate in the coexistence of copper(II), phosphoric acid and ANI yielded an ANIH + salt of Strandberg-type pentamolybdodiphosphate, (ANIH) 2[(PO 4) 2Mo 5O 15{Cu(ANI) 2(H 2O)} 2](ANI)·2H 2O ( 2). These compounds were characterized by elemental analysis, infrared spectroscopy and X-ray single-crystal analysis. The compound 1, crystallizing in trigonal, P3¯,a = 13.883(4), c = 10.187(3) Å, Z = 1, consists of copper mono-substituted Keggin-typed [PCu(H 2O)W 11O 39] 5- anion surrounded by six ANI molecules, of which five are protonated (ANIH +). The compound 2, crystallizing in triclinic, P1¯,a = 13.98(2), b = 14.73(1), c = 16.24(1) Å, α = 111.27(3), β = 97.42(3), γ = 99.54(4)°, Z = 2, consists of Strandberg-type pentamolybdodiphospate [(PO 4) 2Mo 5O 15] 6- anions interconnected by two Cu(ANI) 2(H 2O) linkers to form a 1D-chain structure. A potentiostatic electrolysis of 1 in aqueous solution gave rise to electropolymerization of the ANIH + cations (and ANI) and deposition with the [PCu(H 2O)W 11O 39] 5- anion on an ITO electrode, forming a nano-structured polyaniline/[PCu(H 2O)W 11O 39] 5- hybrid thin film.

  12. 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.

  13. Dietary copper supplements modulate aortic superoxide dismutase, nitric oxide and atherosclerosis.

    PubMed

    Lamb, David J; Tickner, Michelle L; Hourani, Susanna M O; Ferns, Gordon A A

    2005-08-01

    The objective was to test the hypothesis that dietary copper inhibits atherosclerosis by inducing superoxide dismutase (SOD) and potentiating nitric oxide (NO). New Zealand White rabbits were fed either a cholesterol diet (n = 8) or a cholesterol diet containing 0.02% copper acetate (n = 8) for 13 weeks. We found that the intimal area was significantly smaller in the animals supplemented with copper (P < 0.005), although integrated plasma cholesterol levels were not significantly different. This was associated with a significant increase in aortic copper content (P < 0.05), SOD activity (P < 0.05) and Cu/Zn SOD mRNA (P < 0.05) and a significant decrease in nitrotyrosine content (P < 0.05). Furthermore, there was a positive correlation between aortic copper content and SOD activity (P < 0.005, R(2) = 0.83) and a negative correlation between aortic superoxide dimutase activity and nitrotyrosine content (P < 0.005, R(2) = 0.93). In organ bath experiments, the relaxation of precontracted carotid artery rings to calcium ionophore was greater in animals supplemented with copper. No difference in response to sodium nitroprusside was observed. These data suggest that in the cholesterol-fed rabbit, copper supplements inhibit the progression of atherosclerosis by increasing SOD expression, thereby reducing the interaction of NO with superoxide, and hence potentiating NO-mediated pathways that may protect against atherosclerosis.

  14. Dietary copper supplements modulate aortic superoxide dismutase, nitric oxide and atherosclerosis

    PubMed Central

    Lamb, David J; Tickner, Michelle L; Hourani, Susanna M O; Ferns, Gordon A A

    2005-01-01

    The objective was to test the hypothesis that dietary copper inhibits atherosclerosis by inducing superoxide dismutase (SOD) and potentiating nitric oxide (NO). New Zealand White rabbits were fed either a cholesterol diet (n = 8) or a cholesterol diet containing 0.02% copper acetate (n = 8) for 13 weeks. We found that the intimal area was significantly smaller in the animals supplemented with copper (P < 0.005), although integrated plasma cholesterol levels were not significantly different. This was associated with a significant increase in aortic copper content (P < 0.05), SOD activity (P < 0.05) and Cu/Zn SOD mRNA (P < 0.05) and a significant decrease in nitrotyrosine content (P < 0.05). Furthermore, there was a positive correlation between aortic copper content and SOD activity (P < 0.005, R2 = 0.83) and a negative correlation between aortic superoxide dimutase activity and nitrotyrosine content (P < 0.005, R2 = 0.93). In organ bath experiments, the relaxation of precontracted carotid artery rings to calcium ionophore was greater in animals supplemented with copper. No difference in response to sodium nitroprusside was observed. These data suggest that in the cholesterol-fed rabbit, copper supplements inhibit the progression of atherosclerosis by increasing SOD expression, thereby reducing the interaction of NO with superoxide, and hence potentiating NO-mediated pathways that may protect against atherosclerosis. PMID:16045547

  15. 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.

  16. Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

    PubMed

    Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

    2012-10-30

    The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Preslaughter handling effects on pork quality and glycolytic potential in two muscles differing in fiber type composition.

    PubMed

    Hambrecht, E; Eissen, J J; Newman, D J; Smits, C H M; Verstegen, M W A; den Hartog, L A

    2005-04-01

    The objective of the present experiment was to investigate the effects of transportation, lairage, and preslaughter stressor treatment on glycolytic potential and pork quality of the glycolytic longissimus and the oxidative supraspinatus (SSP) or serratus ventralis (SV) muscles. In a 2 x 2 x 2 factorial design, 384 pigs were assigned randomly either to short (50 min) and smooth or long (3 h) and rough transport, long (3 h) or short (< 45 min) lairage, and minimal or high preslaughter stress. Muscle samples were taken from the LM at 135 min and from the SSP at 160 min postmortem for determination of the glycolytic potential and rate of glycolysis. At 23 h postmortem, pork quality was assessed in the LM and the SV. Effects of transport and lairage conditions were similar in both muscle types. Long transport increased (P < 0.01) the glycolytic potential and muscle lactate concentrations compared with short transport. Both long transportation and short lairage decreased (P < 0.01) redness (a* values) and yellowness (b* values) of the LM and SV. In combination with short lairage, long transport decreased (P < 0.05) pork lightness (lower L* values), and electrical conductivity was increased (P < 0.05) after long transport. Several interactions between stress level and muscle type (P < 0.001) were observed. High preslaughter stress decreased (P < 0.001) muscle glycogen in both the LM and SSP, but this decrease was greater in the LM. Lactate concentrations were increased (P < 0.001) only in the LM by high preslaughter stress. Increases in ultimate pH (P < 0.001) and decreases in a* values (P < 0.01) were greatest in the SV, whereas increases in electrical conductivity (P < 0.001) were greatest in the LM. The lack of interactions among transportation, lairage, and muscle type was attributed to the relatively minor differences in stress among treatments. It was concluded that, in glycolytic muscle types such as the LM, the high physical and psychological stress levels associated with stress in the immediate preslaughter period have a greater effect on the water-holding capacity of the meat and may promote PSE development. Conversely, oxidative muscle types tend to have higher ultimate pH values and produce DFD pork in response to intense physical activity and/or high psychological stress levels preslaughter.

  18. Oxidation Mechanism of Copper Selenide

    NASA Astrophysics Data System (ADS)

    Taskinen, Pekka; Patana, Sonja; Kobylin, Petri; Latostenmaa, Petri

    2014-09-01

    The oxidation mechanism of copper selenide was investigated at deselenization temperatures of copper refining anode slimes. The isothermal roasting of synthetic, massive copper selenide in flowing oxygen and oxygen - 20% sulfur dioxide mixtures at 450-550 °C indicate that in both atmospheres the mass of Cu2Se increases as a function of time, due to formation of copper selenite as an intermediate product. Copper selenide oxidises to copper oxides without formation of thick copper selenite scales, and a significant fraction of selenium is vaporized as SeO2(g). The oxidation product scales on Cu2Se are porous which allows transport of atmospheric oxygen to the reaction zone and selenium dioxide vapor to the surrounding gas. Predominance area diagrams of the copper-selenium system, constructed for selenium roasting conditions, indicate that the stable phase of copper in a selenium roaster gas with SO2 is the sulfate CuSO4. The cuprous oxide formed in decomposition of Cu2Se is further sulfated to CuSO4.

  19. Roles of Copper-Binding Proteins in Breast Cancer.

    PubMed

    Blockhuys, Stéphanie; Wittung-Stafshede, Pernilla

    2017-04-20

    Copper ions are needed in several steps of cancer progression. However, the underlying mechanisms, and involved copper-binding proteins, are mainly elusive. Since most copper ions in the body (in and outside cells) are protein-bound, it is important to investigate what copper-binding proteins participate and, for these, how they are loaded with copper by copper transport proteins. Mechanistic information for how some copper-binding proteins, such as extracellular lysyl oxidase (LOX), play roles in cancer have been elucidated but there is still much to learn from a biophysical molecular viewpoint. Here we provide a summary of copper-binding proteins and discuss ones reported to have roles in cancer. We specifically focus on how copper-binding proteins such as mediator of cell motility 1 (MEMO1), LOX, LOX-like proteins, and secreted protein acidic and rich in cysteine (SPARC) modulate breast cancer from molecular and clinical aspects. Because of the importance of copper for invasion/migration processes, which are key components of cancer metastasis, further insights into the actions of copper-binding proteins may provide new targets to combat cancer.

  20. Mechanism of Silver Nanoparticles Action on Insect Pigmentation Reveals Intervention of Copper Homeostasis

    PubMed Central

    Armstrong, Najealicka; Ramamoorthy, Malaisamy; Lyon, Delina; Jones, Kimberly; Duttaroy, Atanu

    2013-01-01

    Silver nanoparticles (AgNPs), like almost all nanoparticles, are potentially toxic beyond a certain concentration because the survival of the organism is compromised due to scores of pathophysiological abnormalities past that concentration. However, the mechanism of AgNP toxicity remains undetermined. Instead of applying a toxic dose, we attempted to monitor the effects of AgNPs at a nonlethal concentration on wild type Drosophila melanogaster by exposing them throughout their development. All adult flies raised in AgNP doped food showed that up to 50 mg/L concentration AgNP has no negative influence on median survival; however, these flies appeared uniformly lighter in body color due to the loss of melanin pigments in their cuticle. Additionally, fertility and vertical movement ability were compromised due to AgNP feeding. Determination of the amount of free ionic silver (Ag+) led us to claim that the observed biological effects have resulted from the AgNPs and not from Ag+. Biochemical analysis suggests that the activity of copper dependent enzymes, namely tyrosinase and Cu-Zn superoxide dismutase, are decreased significantly following the consumption of AgNPs, despite the constant level of copper present in the tissue. Consequently, we propose a mechanism whereby consumption of excess AgNPs in association with membrane bound copper transporter proteins cause sequestration of copper, thus creating a condition that resembles copper starvation. This model also explains the cuticular demelanization effect resulting from AgNP since tyrosinase activity is essential for melanin biosynthesis. Finally, we claim that Drosophila, an established genetic model system, can be well utilized for further understanding of the biological effects of nanoparticles. PMID:23308159

  1. Biological Mechanism of Silver Nanoparticle Toxicity

    NASA Astrophysics Data System (ADS)

    Armstrong, Najealicka Nicole

    Silver nanoparticles (AgNPs), like almost all nanoparticles, are potentially toxic beyond a certain concentration because the survival of the organism is compromised due to scores of pathophysiological abnormalities above that concentration. However, the mechanism of AgNP toxicity remains undetermined. Instead of applying a toxic dose, these investigations were attempted to monitor the effects of AgNPs at a non-lethal concentration on wild type Drosophila melanogaster by exposing them to nanoparticles throughout their development. All adult flies raised in AgNP doped food indicated that of not more than 50 mg/L had no negative influence on median survival; however, these flies appeared uniformly lighter in body color due to the loss of melanin pigments in their cuticle. Additionally, fertility and vertical movement ability were compromised after AgNP feeding. The determination of the amount of free ionic silver (Ag+) indicated that the observed biological effects had resulted from the AgNPs and not from Ag+. Biochemical analysis suggests that the activity of copper dependent enzymes, namely tyrosinase and Cu-Zn superoxide dismutase, were decreased significantly following the consumption of AgNPs, despite the constant level of copper present in the tissue. Furthermore, copper supplementation restored the loss of AgNP induced demelanization, and the reduction of functional Ctr1 in Ctr1 heterozygous mutants caused the flies to be resistant to demelanization. Consequently, these studies proposed a mechanism whereby consumption of excess AgNPs in association with membrane bound copper transporter proteins cause sequestration of copper, thus creating a condition that resembles copper starvation. This model also explained the cuticular demelanization effect resulting from AgNP since tyrosinase activity is essential for melanin biosynthesis. Finally, these investigations demonstrated that Drosophila, an established genetic model system, can be well utilized for further characterizing the biological effects of nanoparticles.

  2. Synthesis of Copper-Antimony-Sulfide Nanocrystals for Solution-Processed Solar Cells.

    PubMed

    Suehiro, Satoshi; Horita, Keisuke; Yuasa, Masayoshi; Tanaka, Tooru; Fujita, Katsuhiko; Ishiwata, Yoichi; Shimanoe, Kengo; Kida, Tetsuya

    2015-08-17

    The p-type nanocrystals (NCs) of copper-based chalcogenides, such as CuInSe2 and Cu2ZnSnS4, have attracted increasing attention in photovoltaic applications due to their potential to produce cheap solution-processed solar cells. Herein, we report the synthesis of copper-antimony-sulfide (CAS) NCs with different crystal phases including CuSbS2, Cu3SbS4, and Cu12Sb4S13. In addition, their morphology, crystal phase, and optical properties were characterized using transmission electron microscopy, X-ray diffractometry, UV-vis-near-IR spectroscopy, and photoemission yield spectroscopy. The morphology, crystal phase, and electronic structure were significantly dependent on the chemical composition in the CAS system. Devices were fabricated using particulate films consisting of CAS NCs prepared by spin coating without a high-temperature treatment. The CAS NC-based devices exhibited a diode-like current-voltage characteristic when coupled with an n-type CdS layer. In particular, the CuSbS2 NC devices exhibited photovoltaic responses under simulated sunlight, demonstrating its applicability for use in solution-processed solar cells.

  3. Properties and characterization of agar/CuNP bionanocomposite films prepared with different copper salts and reducing agents.

    PubMed

    Shankar, Shiv; Teng, Xinnan; Rhim, Jong-Whan

    2014-12-19

    Various types of agar-based bio-nanocomposite (BNC) films were prepared by blending agar and six different copper nanoparticles (CuNPs) with different shapes and sizes obtained from three different sources of copper salts and two different reducing agents. The BNC films were characterized by UV-visible, FE-SEM, FT-IR, and XRD. The thermogravimetric study showed that the melting point of BNC films was increased when ascorbic acid was used as a reducing agent for CuNPs synthesis. Apparent surface color and transmittance of agar film was greatly influenced by the reinforcement of CuNPs. However, mechanical and water vapor barrier properties did not change significantly (p>0.05) by blending with CuNPs. Tensile modulus and tensile strength decreased slightly for all types of CuNPs reinforced while elongation at break slightly increased when CuNPs produced by ascorbic acid were blended. The agar bio-nanocomposite films showed profound antibacterial activity against both Gram-positive and Gram-negative food-borne pathogenic bacteria. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Copper(II) binding by dissolved organic matter: Importance of the copper-to-dissolved organic matter ratio and implications for the Biotic Ligand Model

    USGS Publications Warehouse

    Craven, Alison M.; Aiken, George R.; Ryan, Joseph N.

    2012-01-01

    The ratio of copper to dissolved organic matter (DOM) is known to affect the strength of copper binding by DOM, but previous methods to determine the Cu2+–DOM binding strength have generally not measured binding constants over the same Cu:DOM ratios. In this study, we used a competitive ligand exchange–solid-phase extraction (CLE-SPE) method to determine conditional stability constants for Cu2+–DOM binding at pH 6.6 and 0.01 M ionic strength over a range of Cu:DOM ratios that bridge the detection windows of copper-ion-selective electrode and voltammetry measurements. As the Cu:DOM ratio increased from 0.0005 to 0.1 mg of Cu/mg of DOM, the measured conditional binding constant (cKCuDOM) decreased from 1011.5 to 105.6 M–1. A comparison of the binding constants measured by CLE-SPE with those measured by copper-ion-selective electrode and voltammetry demonstrates that the Cu:DOM ratio is an important factor controlling Cu2+–DOM binding strength even for DOM isolates of different types and different sources and for whole water samples. The results were modeled with Visual MINTEQ and compared to results from the biotic ligand model (BLM). The BLM was found to over-estimate Cu2+ at low total copper concentrations and under-estimate Cu2+ at high total copper concentrations.

  5. Estimation of copper in saliva and areca nut products and its correlation with histological grades of oral submucous fibrosis.

    PubMed

    Mohammed, Faraz; Manohar, Vidya; Jose, Maji; Thapasum, Arishiya Fairozekhan; Mohamed, Shamaz; Shamaz, Bibi Halima; D'Souza, Neevan

    2015-03-01

    The purpose of this study was to estimate the copper levels in saliva of patients with oral submucous fibrosis (OSF) and different areca nut products and its correlation with different histological grades of OSF. The study comprised 60 individuals, 30 OSF patients and 30 non-OSF individuals. Unstimulated whole saliva was collected, and copper analysis was performed using colorimetric method. The commercial areca nut products used by the patients were acquired and subjected to copper analysis through the atomic absorption spectrophotometer method. Oral biopsies were performed for OSF patients for histopathological correlation. The mean salivary copper level was 27.023 μg/dl in OSF patients when compared with 8.393 μg/dl in non-OSF individuals (P < 0.005). The mean copper content in different areca nut products was 13.313 ppm (P < 0.005). Comparison of copper content in different areca nut products with salivary copper levels of OSF patients showed negative correlation (P < 0.853). Comparison of salivary copper levels between different histological grades of OSF yielded a statistically significant association between grades I and III (P < 0.005) and grades II and III OSF (P < 0.019). Comparison of copper content in areca nut products and different histological grades of OSF yielded weak negative statistical correlation (r = -0.116). Despite high copper content in areca nut products, the observations yielded a negative correlation with different histological grades of OSF. This further raises a doubt about the copper content in areca nut as an etiological factor for this crippling disease. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  6. 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

  7. 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.

  8. [Analysis the cupric ion release characteristics of different copper raw materials in intrauterine device in vitro using ICP method].

    PubMed

    Lu, Hua; Ding, Tingting; Yao, Tianping; Sun, Jiao

    2014-05-01

    To study the Cupric ion release characteristics of different copper raw materials in intrauterine device in vitro by ICP. Reveal the relationship between purity and shape of Cu-IUD copper and copper ion release. According to a certain proportion, the copper raw materials were 100 times diluted into the simulated uterine solution at 37 +/- 0.5 degrees C. Replaced medium at certain time points and collected soaking liquid. Using ICP analyzed the concentration of copper ion released. The largest daily release of copper ions was in the first 7 days. There was no statistically significant difference between the copper ion release amount of 99.99% and 99.95% purity copper wire (P > 0.05). The release of copper ion of the copper wire was far greater than that of the copper pipe in early stage (P < 0.01). The release amount decreased and stabilized at 56 day. Release characteristics of copper ion could effectively analysis by ICP. And in the same area, the release amount of copper ions of copper wire was greater than that of copper pipe.

  9. A new preparation of a bifunctional crystalline heterogeneous copper electrocatalyst by electrodeposition using a Robson-type macrocyclic dinuclear copper complex for efficient hydrogen and oxygen evolution from water.

    PubMed

    Majumder, Samit; Abdel Haleem, Ashraf; Nagaraju, Perumandla; Naruta, Yoshinori

    2017-07-18

    The development of low-cost, stable bifunctional electrocatalysts, which operate in the same electrolyte with a low overpotential for water splitting, including the oxygen evolution reaction and the hydrogen evolution reaction, remains an attractive prospect and a great challenge. In this study, a water soluble Robson-type macrocyclic dicopper(ii) complex has been used for the first time as a catalyst precursor for the generation of a copper-based bifunctional heterogeneous catalyst film, which can be used for both HER and OER at a near neutral pH. In sodium borate buffer at pH 9.20, this complex decomposed to give a Cu(OH) 2 /Cu 2 O-based thin film on FTO that catalyzes both hydrogen production and water oxidation. The morphology, nature and composition of the thin film were fully characterized by scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron, and energy dispersive X-ray spectroscopies. The catalyst film showed high stability during the course of electrolysis in either the cathodic or the anodic direction for more than 4 h. Faradaic efficiencies of ∼92% for HER and ∼96% for OER were achieved. The switch between the two half-reactions of catalytic water splitting was fully reversible in nature.

  10. 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...

  11. Long-term effects of copper and pH on the nematode community in an agroecosystem

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

    Korthals, G.W.; Lexmond, T.M.; Kammenga, J.E.

    1996-06-01

    Four copper (0, 250, 500, and 750 kg Cu-ha{sup {minus}1}) and pH (4.0, 4.7, 5.4, and 6.1 in 1 M KCl) treatments were applied to an arable agroecosystem., Effects on the nematode community were assessed after 10 years of exposure under field conditions. Both copper and pH had major influences on nematodes. The effect of copper was generally enhanced with decreasing soil pH. The lowest copper application rate which had a significant negative effect on the total number of nematodes was 250 kg{center_dot}ha{sup {minus}1} at pH 4.0, which is equivalent to a copper concentration of 0.32 mg{center_dot}L{sup {minus}1} in 0.01more » M calcium chloride (Cu-CaCl{sub 2}). Species composition and the abundance of trophic groups were more sensitive than the total number of nematodes. Combinations of high copper and low pH significantly reduced the number of bacterial-feeding nematodes, whereas the number of hyphal-feeding nematodes increased. Omnivorous and predacious nematodes showed the most sensitive response, becoming extinct when Cu-CaCl{sub 2} was 0.8 to 1.4 mg{center_dot}L{sup {minus}1}. Plant-feeding nematodes showed the largest differences in abundance and appeared to reflect the effects of copper and pH on primary production. The results suggest that the nematode community was also affected indirectly by copper and pH via other components of the soil food web. It is concluded that nematodes offer excellent perspectives to assess effects of pollutants at the community level.« less

  12. Biosorption of metal ions from aqueous solutions

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

    Chen, Jiaping; Yiacoumi, Sotira

    1997-01-01

    Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role inmore » the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.« less

  13. Copper deposition in focal nodular hyperplasia and inflammatory hepatocellular adenoma.

    PubMed

    Chandan, Vishal S; Shah, Sejal S; Mounajjed, Taofic; Torbenson, Michael S; Wu, Tsung-Teh

    2018-06-01

    To examine copper deposition in focal nodular hyperplasia (FNH) and inflammatory hepatocellular adenoma (IHA) and to determine if it can play a role in their differentiation. 28 FNHs and 19 IHAs from surgical resections showing typical morphological and immunohistochemical features were stained with rhodanine to evaluate for copper deposition. Histological features such as nodularity, fibrous bands, ductular proliferation, steatosis, ballooned hepatocytes and lymphocytic inflammation were also scored. Copper deposition was detected in 96% (27/28) of FNHs and 37% (7/19) of IHAs, P<0.001. In all cases, copper was seen within the hepatocytes only around the pseudo-portal tracts or areas of fibrosis. Copper deposition in IHA was significantly associated with presence of lymphocytic inflammation (P=0.04) but not associated with features like nodularity, fibrous bands, ductular proliferation, ballooned hepatocytes and steatosis (P>0.05, for all). In FNH, the presence and degree of copper deposition was not significantly associated with any histological features (P>0.05, for all). Copper deposition occurs more frequently in FNH (96%) than IHA (37%), P<0.001. However, the presence of copper alone cannot be used as a feature to differentiate between FNH and IHA. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  14. Molecular imaging and therapy targeting copper metabolism in hepatocellular carcinoma

    PubMed Central

    Wachsmann, Jason; Peng, Fangyu

    2016-01-01

    Hepatocellular carcinoma (HCC) is the fifth most common cancer worldwide. Significant efforts have been devoted to identify new biomarkers for molecular imaging and targeted therapy of HCC. Copper is a nutritional metal required for the function of numerous enzymatic molecules in the metabolic pathways of human cells. Emerging evidence suggests that copper plays a role in cell proliferation and angiogenesis. Increased accumulation of copper ions was detected in tissue samples of HCC and many other cancers in humans. Altered copper metabolism is a new biomarker for molecular cancer imaging with position emission tomography (PET) using radioactive copper as a tracer. It has been reported that extrahepatic mouse hepatoma or HCC xenografts can be localized with PET using copper-64 chloride as a tracer, suggesting that copper metabolism is a new biomarker for the detection of HCC metastasis in areas of low physiological copper uptake. In addition to copper modulation therapy with copper chelators, short-interference RNA specific for human copper transporter 1 (hCtr1) may be used to suppress growth of HCC by blocking increased copper uptake mediated by hCtr1. Furthermore, altered copper metabolism is a promising target for radionuclide therapy of HCC using therapeutic copper radionuclides. Copper metabolism has potential as a new theranostic biomarker for molecular imaging as well as targeted therapy of HCC. PMID:26755872

  15. Effect of paraquat-induced oxidative stress on gene expression and aging of the filamentous ascomycete Podospora anserina

    PubMed Central

    Wiemer, Matthias; Osiewacz, Heinz D.

    2014-01-01

    Aging of biological systems is influenced by various factors, conditions and processes. Among others, processes allowing organisms to deal with various types of stress are of key importance. In particular, oxidative stress as the result of the generation of reactive oxygen species (ROS) at the mitochondrial respiratory chain and the accumulation of ROS-induced molecular damage has been strongly linked to aging. Here we view the impact of ROS from a different angle: their role in the control of gene expression. We report a genome-wide transcriptome analysis of the fungal aging model Podospora anserina grown on medium containing paraquat (PQ). This treatment leads to an increased cellular generation and release of H2O2, a reduced growth rate, and a decrease in lifespan. The combined challenge by PQ and copper has a synergistic negative effect on growth and lifespan. The data from the transcriptome analysis of the wild type cultivated under PQ-stress and their comparison to those of a longitudinal aging study as well as of a copper-uptake longevity mutant of P. anserina revealed that PQ-stress leads to the up-regulation of transcripts coding for components involved in mitochondrial remodeling. PQ also affects the expression of copper-regulated genes suggesting an increase of cytoplasmic copper levels as it has been demonstrated earlier to occur during aging of P. anserina and during senescence of human fibroblasts. This effect may result from the induction of the mitochondrial permeability transition pore via PQ-induced ROS, leading to programmed cell death as part of an evolutionary conserved mechanism involved in biological aging and lifespan control. PMID:28357247

  16. Influence of metallic vapours on thermodynamic and transport properties of two-temperature air plasma

    NASA Astrophysics Data System (ADS)

    Zhong, Linlin; Wang, Xiaohua; Cressault, Yann; Teulet, Philippe; Rong, Mingzhe

    2016-09-01

    The metallic vapours (i.e., copper, iron, and silver in this paper) resulting from walls and/or electrode surfaces can significantly affect the characteristics of air plasma. Different from the previous works assuming local thermodynamic equilibrium, this paper investigates the influence of metallic vapours on two-temperature (2 T) air plasma. The 2 T compositions of air contaminated by Cu, Fe, and Ag are first determined based on Saha's and Guldberg-Waage's laws. The thermodynamic properties (including mass density, specific enthalpy, and specific heat) are then calculated according to their definitions. After determining the collision integrals for each pair of species in air-metal mixtures using the newly published methods and source data, the transport coefficients (including electrical conductivity, viscosity, and thermal conductivity) are calculated for air-Cu, air-Fe, and air-Ag plasmas with different non-equilibrium degree θ (Te/Th). The influences of metallic contamination as well as non-equilibrium degree are discussed. It is found that copper, iron, and silver exist mainly in the form of Cu2, FeO, and AgO at low temperatures. Generally, the metallic vapours increase mass density at most temperatures, reduce the specific enthalpy and specific heat in the whole temperature range, and affect the transport properties remarkably from 5000 K to 20 000 K. The effect arising from the type of metals is little except for silver at certain temperatures. Besides, the departure from thermal equilibrium results in the delay of dissociation and ionization reactions, leading to the shift of thermodynamic and transport properties towards a higher temperature.

  17. The metal chaperone Atox1 regulates the activity of the human copper transporter ATP7B by modulating domain dynamics.

    PubMed

    Yu, Corey H; Yang, Nan; Bothe, Jameson; Tonelli, Marco; Nokhrin, Sergiy; Dolgova, Natalia V; Braiterman, Lelita; Lutsenko, Svetlana; Dmitriev, Oleg Y

    2017-11-03

    The human transporter ATP7B delivers copper to the biosynthetic pathways and maintains copper homeostasis in the liver. Mutations in ATP7B cause the potentially fatal hepatoneurological disorder Wilson disease. The activity and intracellular localization of ATP7B are regulated by copper, but the molecular mechanism of this regulation is largely unknown. We show that the copper chaperone Atox1, which delivers copper to ATP7B, and the group of the first three metal-binding domains (MBD1-3) are central to the activity regulation of ATP7B. Atox1-Cu binding to ATP7B changes domain dynamics and interactions within the MBD1-3 group and activates ATP hydrolysis. To understand the mechanism linking Atox1-MBD interactions and enzyme activity, we have determined the MBD1-3 conformational space using small angle X-ray scattering and identified changes in MBD dynamics caused by apo -Atox1 and Atox1-Cu by solution NMR. The results show that copper transfer from Atox1 decreases domain interactions within the MBD1-3 group and increases the mobility of the individual domains. The N-terminal segment of MBD1-3 was found to interact with the nucleotide-binding domain of ATP7B, thus physically coupling the domains involved in copper binding and those involved in ATP hydrolysis. Taken together, the data suggest a regulatory mechanism in which Atox1-mediated copper transfer activates ATP7B by releasing inhibitory constraints through increased freedom of MBD1-3 motions. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. Defect studies in copper-based p-type transparent conducting oxides

    NASA Astrophysics Data System (ADS)

    Ameena, Fnu

    Among other intrinsic open-volume defects, copper vacancy (VCu) has been theoretically identified as the major acceptor in p-type Cu-based semiconducting transparent oxides, which has potential as low-cost photovoltaic absorbers in semi-transparent solar cells. A series of positron annihilation experiments with pure Cu, Cu2O, and CuO presented strong presence of VCu and its complexes in the copper oxides. The lifetime data also showed that the density of VCu was becoming higher as the oxidation state of Cu increased which was consistent with the decrease in the formation energy of VCu. Doppler broadening measurements further indicated that electrons with low momentum made more contribution to the contributed as pure Cu oxidizes to copper oxides. The metastable defects are known to be generated in Cu2O upon illumination and it has been known to affect the performance of Cu2O-based hetero-junctions used in solar cells. The metastable effect was studied using positron annihilation lifetime spectroscopy and its data showed the change in the defect population upon light exposure and the minimal effect of light-induced electron density increase in the bulk of materials to the average lifetime of the positrons. The change in the defect population is concluded to be related to the dissociation and association of VCu -- V Cu complexes. For example, the shorter lifetime under light was ascribed to the annihilation with smaller size vacancies, which explains the dissociation of the complexes with light illumination. Doppler broadening of the annihilation was independent of light illumination, which suggested that the chemical nature of the defects remained without change upon their dissociation and association -- only the size distribution of copper vacancies varied. The delafossite metal oxides, CuMIIIO2 are emerging wide-bandgap p-type semiconductors. In this research, the formation energies of structural vacancies are calculated using Van Vechten cavity model as an attempt to study the effect of the size of the MIII cation in the delafossites starting from Cu2O. Comparison of the formation energies between Cu2O and delafossite oxides clearly showed that the equilibrium concentration of the vacancies depended strongly on the structural parameters varied by the presence of different MIII cations. In particular, the size of the MIII cation greatly influenced the defect formation energies of VCu. It was observed from our calculations, as the size increases the formation energy decreases.

  19. High-Efficiency Fullerene Solar Cells Enabled by a Spontaneously Formed Mesostructured CuSCN-Nanowire Heterointerface.

    PubMed

    Sit, Wai-Yu; Eisner, Flurin D; Lin, Yen-Hung; Firdaus, Yuliar; Seitkhan, Akmaral; Balawi, Ahmed H; Laquai, Frédéric; Burgess, Claire H; McLachlan, Martyn A; Volonakis, George; Giustino, Feliciano; Anthopoulos, Thomas D

    2018-04-01

    Fullerenes and their derivatives are widely used as electron acceptors in bulk-heterojunction organic solar cells as they combine high electron mobility with good solubility and miscibility with relevant semiconducting polymers. However, studies on the use of fullerenes as the sole photogeneration and charge-carrier material are scarce. Here, a new type of solution-processed small-molecule solar cell based on the two most commonly used methanofullerenes, namely [6,6]-phenyl-C61-butyric acid methyl ester (PC 60 BM) and [6,6]-phenyl-C71-butyric acid methyl ester (PC 70 BM), as the light absorbing materials, is reported. First, it is shown that both fullerene derivatives exhibit excellent ambipolar charge transport with balanced hole and electron mobilities. When the two derivatives are spin-coated over the wide bandgap p-type semiconductor copper (I) thiocyanate (CuSCN), cells with power conversion efficiency (PCE) of ≈1%, are obtained. Blending the CuSCN with PC 70 BM is shown to increase the performance further yielding cells with an open-circuit voltage of ≈0.93 V and a PCE of 5.4%. Microstructural analysis reveals that the key to this success is the spontaneous formation of a unique mesostructured p-n-like heterointerface between CuSCN and PC 70 BM. The findings pave the way to an exciting new class of single photoactive material based solar cells.

  20. Two Silene vulgaris copper transporters residing in different cellular compartments confer copper hypertolerance by distinct mechanisms when expressed in Arabidopsis thaliana.

    PubMed

    Li, Yanbang; Iqbal, Mazhar; Zhang, Qianqian; Spelt, Cornelis; Bliek, Mattijs; Hakvoort, Henk W J; Quattrocchio, Francesca M; Koes, Ronald; Schat, Henk

    2017-08-01

    Silene vulgaris is a metallophyte of calamine, cupriferous and serpentine soils all over Europe. Its metallicolous populations are hypertolerant to zinc (Zn), cadmium (Cd), copper (Cu) or nickel (Ni), compared with conspecific nonmetallicolous populations. These hypertolerances are metal-specific, but the underlying mechanisms are poorly understood. We investigated the role of HMA5 copper transporters in Cu-hypertolerance of a S. vulgaris copper mine population. Cu-hypertolerance in Silene is correlated and genetically linked with enhanced expression of two HMA5 paralogs, SvHMA5I and SvHMA5II, each of which increases Cu tolerance when expressed in Arabidopsis thaliana. Most Spermatophytes, except Brassicaceae, possess homologs of SvHMA5I and SvHMA5II, which originate from an ancient duplication predating the appearance of spermatophytes. SvHMA5II and the A. thaliana homolog AtHMA5 localize in the endoplasmic reticulum and upon Cu exposure move to the plasma membrane, from where they are internalized and degraded in the vacuole. This resembles trafficking of mammalian homologs and is apparently an extremely ancient mechanism. SvHMA5I, instead, neofunctionalized and always resides on the tonoplast, likely sequestering Cu in the vacuole. Adaption of Silene to a Cu-polluted soil is at least in part due to upregulation of two distinct HMA5 transporters, which contribute to Cu hypertolerance by distinct mechanisms. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

  1. Featured Article: Effect of copper on nuclear translocation of copper chaperone for superoxide dismutase-1

    PubMed Central

    Wang, Lin; Ge, Yan

    2016-01-01

    Copper chaperone for superoxide dismutase-1 (CCS-1), facilitating copper insertion into superoxide dismutase 1 (SOD-1), is present in the nucleus. However, it is unknown how CCS-1 is translocated to the nucleus. The present study was undertaken to determine the effect of copper on nuclear translocation of CCS-1. Human umbilical vein endothelial cells (HUVECs) were subjected to hypoxia, causing an increase in both copper and CCS-1 in the nucleus. Treatment with tetraethylenepentamine (TEPA) not only decreased the total cellular concentration and the nuclear translocation of copper, but also completely suppressed the entry of CCS-1 to the nucleus. On the other hand, siRNA targeting CCS-1 neither inhibited the increase in total concentrations nor blocked the nuclear translocation of copper. This study thus demonstrates that under hypoxia condition, both copper and CCS-1 are transported to the nucleus. The nuclear translocation of CCS-1 is copper dependent, but the nuclear translocation of copper could take place alternatively in a CCS-1-independent pathway. PMID:27190267

  2. Response to excess copper in the hyperthermophile Sulfolobus solfataricus strain 98/2

    PubMed Central

    Villafane, Aramis; Voskoboynik, Yekaterina; Cuebas, Mariola; Ruhl, Ilona; Bini, Elisabetta

    2009-01-01

    Copper is an essential micronutrient, but toxic in excess. Sulfolobus solfataricus cells have the ability to adapt to fluctuations of copper levels in their external environment. To better understand the molecular mechanism behind the organismal response to copper, the expression of the cluster of genes copRTA, which encodes the copper-responsive transcriptional regulator CopR, the copper-binding protein CopT, and CopA, has been investigated and the whole operon has been shown to be cotranscribed at low levels from the copR promoter under all conditions, whereas increased transcription from the copTA promoter occurs in the presence of excess copper. Furthermore, the expression of the copper-transporting ATPase CopA over a 27-hour interval has been monitored by quantitative real-time RT-PCR and compared to the pattern of cellular copper accumulation, as determined in a parallel analysis by Inductively Coupled Plasma Optical Emission spectrometry (ICP-OES). The results provide the basis for a model of the molecular mechanisms of copper homeostasis in Sulfolobus, which relies on copper efflux and sequestration. PMID:19427833

  3. Modulation of cholesterol levels in broiler meat by dietary garlic and copper.

    PubMed

    Konjufca, V H; Pesti, G M; Bakalli, R I

    1997-09-01

    Male Ross x Ross 208 chickens were fed from hatching to 21 d of age either a control diet (based on corn and soybean meal) or the control diet supplemented with 0, 1.5, 3.0, and 4.5% of a commercial garlic powder in Experiments 1 and 2. Once the dose-response relationship was established, 3% garlic powder or 63 or 180 mg/kg copper as cupric citrate or cupric sulfate pentahydrate were supplemented to the diet (Experiments 3, 4, 5, and 6). In the first two experiments, reductions of plasma cholesterol (P = 0.006) and triacylglycerols (P = 0.013) and liver (P = 0.012) and breast muscle (P = 0.165) cholesterol were observed in garlic-supplemented birds. Feeding either garlic powder or copper (63 and 180 mg/kg) resulted in reduced levels of plasma cholesterol, liver cholesterol, blood reduced glutathione, and breast and thigh muscle cholesterol. Differences were significant at P < 0.05 in at least one experiment. 3-Hydroxy-3-methylglutaryl reductase activity was decreased due to dietary garlic (P = 0.0369), but not by pharmacological levels of dietary copper (P = 0.982). The activity of fatty acid synthetase was decreased in birds fed copper (P = 0.035). Both garlic and copper supplements decreased cholesterol 7 alpha-hydroxylase activity (P = 0.024 and P = 0.022, respectively). The results of these trials confirm the findings that garlic and copper alter lipid and cholesterol metabolism. However, they do not work by the same mechanism. Feeding dietary garlic or copper for 21 d reduced cholesterol levels of broiler meat without altering growth of the chickens or feed efficiency.

  4. Uncovering the transmembrane metal binding site of the novel bacterial major facilitator superfamily-type copper importer CcoA

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

    Khalfaoui-Hassani, Bahia; Verissimo, Andreia F.; Koch, Hans -Georg

    In this study, uptake and trafficking of metals and their delivery to their respective metalloproteins are important processes. Cells need precise control of each step to avoid exposure to excessive metal concentrations and their harmful consequences. Copper (Cu) is a required micronutrient used as a cofactor in proteins. However, in large amounts, it can induce oxidative damage; hence, Cu homeostasis is indispensable for cell survival. Biogenesis of respiratory heme-Cu oxygen (HCO) reductases includes insertion of Cu into their catalytic subunits to form heme-Cu binuclear centers. Previously, we had shown that CcoA is a major facilitator superfamily (MFS)-type bacterial Cu importermore » required for biogenesis of cbb 3-type cytochrome coxidase ( cbb 3-Cox). Here, using Rhodobacter capsulatus, we focused on the import and delivery of Cu to cbb 3-Cox. By comparing the CcoA amino acid sequence with its homologues from other bacterial species, we located several well-conserved Met, His, and Tyr residues that might be important for Cu transport. We determined the topology of the transmembrane helices that carry these residues to establish that they are membrane embedded, and substituted for them amino acids that do not ligand metal atoms. Characterization of these mutants for their uptake of radioactive 64Cu and cbb 3-Cox activities demonstrated that Met233 and His261 of CcoA are essential and Met237 and Met265 are important, whereas Tyr230 has no role for Cu uptake or cbb3-Cox biogenesis. These findings show for the first time that CcoA-mediated Cu import relies on conserved Met and His residues that could act as metal ligands at the membrane-embedded Cu binding domain of this transporter.« less

  5. Uncovering the transmembrane metal binding site of the novel bacterial major facilitator superfamily-type copper importer CcoA

    DOE PAGES

    Khalfaoui-Hassani, Bahia; Verissimo, Andreia F.; Koch, Hans -Georg; ...

    2016-01-19

    In this study, uptake and trafficking of metals and their delivery to their respective metalloproteins are important processes. Cells need precise control of each step to avoid exposure to excessive metal concentrations and their harmful consequences. Copper (Cu) is a required micronutrient used as a cofactor in proteins. However, in large amounts, it can induce oxidative damage; hence, Cu homeostasis is indispensable for cell survival. Biogenesis of respiratory heme-Cu oxygen (HCO) reductases includes insertion of Cu into their catalytic subunits to form heme-Cu binuclear centers. Previously, we had shown that CcoA is a major facilitator superfamily (MFS)-type bacterial Cu importermore » required for biogenesis of cbb 3-type cytochrome coxidase ( cbb 3-Cox). Here, using Rhodobacter capsulatus, we focused on the import and delivery of Cu to cbb 3-Cox. By comparing the CcoA amino acid sequence with its homologues from other bacterial species, we located several well-conserved Met, His, and Tyr residues that might be important for Cu transport. We determined the topology of the transmembrane helices that carry these residues to establish that they are membrane embedded, and substituted for them amino acids that do not ligand metal atoms. Characterization of these mutants for their uptake of radioactive 64Cu and cbb 3-Cox activities demonstrated that Met233 and His261 of CcoA are essential and Met237 and Met265 are important, whereas Tyr230 has no role for Cu uptake or cbb3-Cox biogenesis. These findings show for the first time that CcoA-mediated Cu import relies on conserved Met and His residues that could act as metal ligands at the membrane-embedded Cu binding domain of this transporter.« less

  6. Effects of copper on the antioxidant activity of olive polyphenols in bulk oil and oil-in-water emulsions.

    PubMed

    Paiva-Martins, Fátima; Santos, Vera; Mangericão, Hugo; Gordon, Michael H

    2006-05-17

    The antioxidant activity and interactions with copper of four olive oil phenolic compounds, namely oleuropein, hydroxytyrosol, 3,4-dihydroxyphenylethanol-elenolic acid (1), and 3,4-dihydroxyphenylethanol-elenolic acid dialdehyde (2), in olive oil and oil-in-water emulsions stored at 60 degrees C were studied. All four phenolic compounds significantly extended the induction time of lipid oxidation in olive oil with the order of activity being hydroxytyrosol > compound 1 > compound 2 > oleuropein > alpha-tocopherol; but in the presence of Cu(ll), the stability of oil samples containing phenolic compounds decreased by at least 90%, and the antioxidant activity of hydroxytyrosol and compounds 1 and 2 became similar. In oil-in-water emulsions prepared from olive oil stripped of tocopherols, hydroxytyrosol enhanced the prooxidant effect of copper at pH 5.5 but not at pH 7.4. The stability of samples containing copper at pH 5.5 was not significantly different if oleuropein was present from that of the control. Oleuropein at pH 7.4, and compounds 1 and 2 at both pH values tested, reduced the prooxidant effect of copper. The lower stability and the higher reducing capacity of all compounds at pH 7.4 could not explain the higher stability of emulsions containing phenolic compounds at this pH value. However, mixtures containing hydroxytyrosol or oleuropein with copper showed higher 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity at pH 7.4 than at pH 5.5. Moreover, the compound 2-copper complex showed higher radical scavenging activity then the uncomplexed compound at pH 5.5. It can be concluded that the formation of a copper complex with radical scavenging activity is a key step in the antioxidant action of the olive oil phenolic compounds in an emulsion containing copper ions.

  7. 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

  8. Juvenile roach (Rutilus rutilus) increase their anaerobic metabolism in response to copper exposure in laboratory conditions.

    PubMed

    Maes, Virginie; Betoulle, Stéphane; Jaffal, Ali; Dedourge-Geffard, Odile; Delahaut, Laurence; Geffard, Alain; Palluel, Olivier; Sanchez, Wilfried; Paris-Palacios, Séverine; Vettier, Aurélie; David, Elise

    2016-07-01

    This study aims to determine the potential impairment of cell energy synthesis processes (glycolysis and respiratory chain pathways) by copper in juvenile roach at different regulation levels by using a multi-marker approach. Juvenile roach were exposed to 0, 10, 50, and 100 µg/L of copper for 7 days in laboratory conditions. The glycolysis pathway was assessed by measuring the relative expression levels of 4 genes encoding glycolysis enzymes. The respiratory chain was studied by assessing the electron transport system and cytochrome c oxidase gene expression. Muscle mitochondria ultrastructure was studied, and antioxidant responses were measured. Furthermore, the main energy reserves-carbohydrates, lipids, and proteins-were measured, and cellular energy was evaluated by measuring ATP, ADP, AMP and IMP concentrations. This study revealed a disturbance of the cell energy metabolism due to copper exposure, with a significant decrease in adenylate energy charge in roach exposed to 10 μg/L of copper after 1 day. Moreover, ATP concentrations significantly decreased in roach exposed to 10 μg/L of copper after 1 day. This significant decrease persisted in roach exposed to 50 µg/L of copper after 7 days. AMP concentrations increased in all contaminated fish after 1 day of exposure. In parallel, the relative expression of 3 genes encoding for glycolysis enzymes increased in all contaminated fish after 1 day of copper exposure. Focusing on the respiratory chain, cytochrome c oxidase gene expression also increased in all contaminated fish at the two time-points. The activity of the electron transport system was not disturbed by copper, except in roach exposed to 100 µg/L of copper after 1 day. Copper induced a metabolic stress. Juvenile roach seemed to respond to the ensuing high energy demand by increasing their anaerobic metabolism, but the energy produced by the anaerobic metabolism is unable to compensate for the stress induced by copper after 7 days. This multi-marker approach allows us to reach a greater understanding of the effects of copper on the physiological responses of juvenile roach.

  9. Hydrogen transport behavior of metal coatings for plasma-facing components

    NASA Astrophysics Data System (ADS)

    Anderl, R. A.; Holland, D. F.; Longhurst, G. R.

    1990-12-01

    Plasma-facing components for experimental and commercial fusion reactor studies may include cladding or coatings of refractory metals like tungsten on metallic structural substrates such as copper, vanadium alloys and austenitic stainless steel. Issues of safety and fuel economy include the potential for inventory buildup and permeation of tritium implanted into the plasma-facing surface. This paper reports on laboratory-scale studies with 3 keV D +3 ion beams to investigate the hydrogen transport behavior in tungsten coatings on substrates of copper. These experiments entailed measurements of the deuterium re-emission and permeation rates for tungsten, copper, and tungsten-coated copper specimens at temperatures ranging from 638 to 825 K and implanting particle fluxes of approximately 5 × 10 19 D/m 2 s. Diffusion constants and surface recombination coefficients with enhancement factors due to sputtering were obtained from these measurements. These data may be used in calculations to estimate permeation rates and inventory buildups for proposed diverter designs.

  10. P-type ATPases as drug targets: tools for medicine and science.

    PubMed

    Yatime, Laure; Buch-Pedersen, Morten J; Musgaard, Maria; Morth, J Preben; Lund Winther, Anne-Marie; Pedersen, Bjørn P; Olesen, Claus; Andersen, Jens Peter; Vilsen, Bente; Schiøtt, Birgit; Palmgren, Michael G; Møller, Jesper V; Nissen, Poul; Fedosova, Natalya

    2009-04-01

    P-type ATPases catalyze the selective active transport of ions like H+, Na+, K+, Ca2+, Zn2+, and Cu2+ across diverse biological membrane systems. Many members of the P-type ATPase protein family, such as the Na+,K+-, H+,K+-, Ca2+-, and H+-ATPases, are involved in the development of pathophysiological conditions or provide critical function to pathogens. Therefore, they seem to be promising targets for future drugs and novel antifungal agents and herbicides. Here, we review the current knowledge about P-type ATPase inhibitors and their present use as tools in science, medicine, and biotechnology. Recent structural information on a variety of P-type ATPase family members signifies that all P-type ATPases can be expected to share a similar basic structure and a similar basic machinery of ion transport. The ion transport pathway crossing the membrane lipid bilayer is constructed of two access channels leading from either side of the membrane to the ion binding sites at a central cavity. The selective opening and closure of the access channels allows vectorial access/release of ions from the binding sites. Recent structural information along with new homology modeling of diverse P-type ATPases in complex with known ligands demonstrate that the most proficient way for the development of efficient and selective drugs is to target their ion transport pathway.

  11. Strategic Industry Attack.

    DTIC Science & Technology

    1980-01-15

    Code B364078464 V99QAXNH30303 H2590D. IS KEY WORDS fCo.. e.1 Odn Od It -C.eWV WHO Idnlif b 61-k n 0ber) Strategic Targeting Copper Industry INDATAK 20...develop, debug and test an industrial simulation model (INDATAK) using the LOGATAK model as a point of departure. The copper processing industry is...significant processes in the copper industry, including the transportation network connecting the processing elements, have been formatted for use in

  12. Effects of roof and rainwater characteristics on copper concentrations in roof runoff.

    PubMed

    Bielmyer, Gretchen K; Arnold, W Ray; Tomasso, Joseph R; Isely, Jeff J; Klaine, Stephen J

    2012-05-01

    Copper sheeting is a common roofing material used in many parts of the world. However, copper dissolved from roof sheeting represents a source of copper ions to watersheds. Researchers have studied and recently developed a simple and efficient model to predict copper runoff rates. Important input parameters include precipitation amount, rain pH, and roof angle. We hypothesized that the length of a roof also positively correlates with copper concentration (thus, runoff rates) on the basis that runoff concentrations should positively correlate with contact time between acidic rain and the copper sheet. In this study, a novel system was designed to test and model the effects of roof length (length of roof from crown to the drip edge) on runoff copper concentrations relative to rain pH and roof angle. The system consisted of a flat-bottom copper trough mounted on an apparatus that allowed run length and slope to be varied. Water of known chemistry was trickled down the trough at a constant rate and sampled at the bottom. Consistent with other studies, as pH of the synthetic rainwater decreased, runoff copper concentrations increased. At all pH values tested, these results indicated that run length was more important in explaining variability in copper concentrations than was the roof slope. The regression equation with log-transformed data (R(2) = 0.873) accounted for slightly more variability than the equation with untransformed data (R(2) = 0.834). In log-transformed data, roof angle was not significant in predicting copper concentrations.

  13. INFLUENCE OF PH AND REDOX CONDITIONS ON COPPER LEACHING

    EPA Science Inventory

    Leaching behavior of metals from a mineral processing waste at varying pH and redox conditions was studies. Effect of combinations of pH and Eh on leaching of copper is described. Leaching of copper was found to be dependent on both pH and Eh. Higher concentrations of Cu were ...

  14. Rapid and reliable diagnosis of Wilson disease using X-ray fluorescence.

    PubMed

    Kaščáková, Slávka; Kewish, Cameron M; Rouzière, Stéphan; Schmitt, Françoise; Sobesky, Rodolphe; Poupon, Joël; Sandt, Christophe; Francou, Bruno; Somogyi, Andrea; Samuel, Didier; Jacquemin, Emmanuel; Dubart-Kupperschmitt, Anne; Nguyen, Tuan Huy; Bazin, Dominique; Duclos-Vallée, Jean-Charles; Guettier, Catherine; Le Naour, François

    2016-07-01

    Wilson's disease (WD) is a rare autosomal recessive disease due to mutations of the gene encoding the copper-transporter ATP7B. The diagnosis is hampered by the variability of symptoms induced by copper accumulation, the inconstancy of the pathognomonic signs and the absence of a reliable diagnostic test. We investigated the diagnostic potential of X-ray fluorescence (XRF) that allows quantitative analysis of multiple elements. Studies were performed on animal models using Wistar rats (n = 10) and Long Evans Cinnamon (LEC) rats (n = 11), and on human samples including normal livers (n = 10), alcohol cirrhosis (n = 8), haemochromatosis (n = 10), cholestasis (n = 6) and WD (n = 22). XRF experiments were first performed using synchrotron radiation to address the elemental composition at the cellular level. High-resolution mapping of tissue sections allowed measurement of the intensity and the distribution of copper, iron and zinc while preserving the morphology. Investigations were further conducted using a laboratory X-ray source for irradiating whole pieces of tissue. The sensitivity of XRF was highlighted by the discrimination of LEC rats from wild type even under a regimen using copper deficient food. XRF on whole formalin-fixed paraffin embedded needle biopsies allowed profiling of the elements in a few minutes. The intensity of copper related to iron and zinc significantly discriminated WD from other genetic or chronic liver diseases with 97.6% specificity and 100% sensitivity. This study established a definite diagnosis of Wilson's disease based on XRF. This rapid and versatile method can be easily implemented in a clinical setting.

  15. 40 CFR 415.365 - New source performance standards (NSPS).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... GUIDELINES AND STANDARDS INORGANIC CHEMICALS MANUFACTURING POINT SOURCE CATEGORY Copper Salts Production... producing copper sulfate, copper chloride, copper iodide, or copper nitrate must achieve the following new source performance standards (NSPS): The limitations for pH, TSS, copper (T), nickel (T), and selenium (T...

  16. 40 CFR 415.365 - New source performance standards (NSPS).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... GUIDELINES AND STANDARDS INORGANIC CHEMICALS MANUFACTURING POINT SOURCE CATEGORY Copper Salts Production... producing copper sulfate, copper chloride, copper iodide, or copper nitrate must achieve the following new source performance standards (NSPS): The limitations for pH, TSS, copper (T), nickel (T), and selenium (T...

  17. All-inorganic large-area low-cost and durable flexible perovskite solar cells using copper foil as a substrate.

    PubMed

    Abdollahi Nejand, B; Nazari, P; Gharibzadeh, S; Ahmadi, V; Moshaii, A

    2017-01-05

    Here, a low-cost perovskite solar cell using CuI and ZnO as the respective inorganic hole and electron transport layers is introduced. Copper foil is chosen as a cheap and low-weight conductive substrate which has a similar work function to ITO. Besides, copper foil is an interesting copper atom source for the growth of the upper cuprous iodide layer on copper foil. A spray coating of a transparent silver nanowire electrode is used as a top contact. The prepared device shows a maximum power conversion efficiency of 12.80% and long-term durability providing an environmentally and market friendly perovskite solar cell.

  18. The structural flexibility of the human copper chaperone Atox1: Insights from combined pulsed EPR studies and computations.

    PubMed

    Levy, Ariel R; Turgeman, Meital; Gevorkyan-Aiapetov, Lada; Ruthstein, Sharon

    2017-08-01

    Metallochaperones are responsible for shuttling metal ions to target proteins. Thus, a metallochaperone's structure must be sufficiently flexible both to hold onto its ion while traversing the cytoplasm and to transfer the ion to or from a partner protein. Here, we sought to shed light on the structure of Atox1, a metallochaperone involved in the human copper regulation system. Atox1 shuttles copper ions from the main copper transporter, Ctr1, to the ATP7b transporter in the Golgi apparatus. Conventional biophysical tools such as X-ray or NMR cannot always target the various conformational states of metallochaperones, owing to a requirement for crystallography or low sensitivity and resolution. Electron paramagnetic resonance (EPR) spectroscopy has recently emerged as a powerful tool for resolving biological reactions and mechanisms in solution. When coupled with computational methods, EPR with site-directed spin labeling and nanoscale distance measurements can provide structural information on a protein or protein complex in solution. We use these methods to show that Atox1 can accommodate at least four different conformations in the apo state (unbound to copper), and two different conformations in the holo state (bound to copper). We also demonstrate that the structure of Atox1 in the holo form is more compact than in the apo form. Our data provide insight regarding the structural mechanisms through which Atox1 can fulfill its dual role of copper binding and transfer. © 2017 The Protein Society.

  19. 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.

  20. The trade-off of availability and growth inhibition through copper for the production of copper-dependent enzymes by Pichia pastoris.

    PubMed

    Balakumaran, Palanisamy Athiyaman; Förster, Jan; Zimmermann, Martin; Charumathi, Jayachandran; Schmitz, Andreas; Czarnotta, Eik; Lehnen, Mathias; Sudarsan, Suresh; Ebert, Birgitta E; Blank, Lars Mathias; Meenakshisundaram, Sankaranarayanan

    2016-02-20

    Copper is an essential chemical element for life as it is a part of prosthetic groups of enzymes including super oxide dismutase and cytochrome c oxidase; however, it is also toxic at high concentrations. Here, we present the trade-off of copper availability and growth inhibition of a common host used for copper-dependent protein production, Pichia pastoris. At copper concentrations ranging from 0.1 mM (6.35 mg/L) to 2 mM (127 mg/L), growth rates of 0.25 h(-1) to 0.16 h(-1) were observed with copper uptake of as high as 20 mgcopper/gCDW. The intracellular copper content was estimated by subtracting the copper adsorbed on the cell wall from the total copper concentration in the biomass. Higher copper concentrations led to stronger cell growth retardation and, at 10 mM (635 mg/L) and above, to growth inhibition. To test the determined copper concentration range for optimal recombinant protein production, a laccase gene from Aspergillus clavatus [EMBL: EAW07265.1] was cloned under the control of the constitutive glyceraldehyde-3-phosphate (GAP) dehydrogenase promoter for expression in P. pastoris. Notably, in the presence of copper, laccase expression improved the specific growth rate of P. pastoris. Although copper concentrations of 0.1 mM and 0.2 mM augmented laccase expression 4 times up to 3 U/mL compared to the control (0.75 U/mL), while higher copper concentrations resulted in reduced laccase production. An intracellular copper content between 1 and 2 mgcopper/gCDW was sufficient for increased laccase activity. The physiology of the yeast could be excluded as a reason for the stop of laccase production at moderate copper concentrations as no flux redistribution could be observed by (13)C-metabolic flux analysis. Copper and its pivotal role to sustain cellular functions is noteworthy. However, knowledge on its cellular accumulation, availability and distribution for recombinant protein production is limited. This study attempts to address one such challenge, which revealed the fact that intracellular copper accumulation influenced laccase production and should be considered for high protein expression of copper-dependent enzymes when using P. pastoris. The results are discussed in the context of P. pastoris as a general host for copper -dependent enzyme production.

  1. Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins

    PubMed Central

    Lancaster, Kyle M.; Zaballa, María-Eugenia; Sproules, Stephen; Sundararajan, Mahesh; DeBeer, Serena; Richards, John H.; Vila, Alejandro J.; Neese, Frank; Gray, Harry B.

    2016-01-01

    Bioinorganic canon states that active-site thiolate coordination promotes rapid electron transfer (ET) to and from type 1 copper proteins. In recent work, we have found that copper ET sites in proteins also can be constructed without thiolate ligation (called “type zero” sites). Here we report multifrequency electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), and nuclear magnetic resonance (NMR) spectroscopic data together with density functional theory (DFT) and spectroscopy-oriented configuration interaction (SORCI) calculations for type zero Pseudomonas aeruginosa azurin variants. Wild-type (type 1) and type zero copper centers experience virtually identical ligand fields. Moreover, O-donor covalency is enhanced in type zero centers relative that in the C112D (type 2) protein. At the same time, N-donor covalency is reduced in a similar fashion to type 1 centers. QM/MM and SORCI calculations show that the electronic structures of type zero and type 2 are intimately linked to the orientation and coordination mode of the carboxylate ligand, which in turn is influenced by outer-sphere hydrogen bonding. PMID:22563915

  2. The MCNP-4C2 design of a two element photon/electron dosemeter that uses magnesium/copper/phosphorus doped lithium fluoride.

    PubMed

    Eakins, J S; Bartlett, D T; Hager, L G; Molinos-Solsona, C; Tanner, R J

    2008-01-01

    The Health Protection Agency is changing from using detectors made from 7LiF:Mg,Ti in its photon/electron personal dosemeters, to 7LiF:Mg,Cu,P. Specifically, the Harshaw TLD-700H card is to be adopted. As a consequence of this change, the dosemeter holder is also being modified not only to accommodate the shape of the new card, but also to optimize the photon and electron response characteristics of the device. This redesign process was achieved using MCNP-4C2 and the kerma approximation, electron range/energy tables with additional electron transport calculations, and experimental validation, with different potential filters compared; the optimum filter studied was a polytetrafluoroethylene disc of diameter 18 mm and thickness 4.3 mm. Calculated relative response characteristics at different angles of incidence and energies between 16 and 6174 keV are presented for this new dosemeter configuration and compared with measured type-test results. A new estimate for the energy-dependent relative light conversion efficiency appropriate to the 7LiF:Mg,Cu,P was also derived for determining the correct dosemeter response.

  3. Copper-2 Ingestion, Plus Increased Meat Eating Leading to Increased Copper Absorption, Are Major Factors Behind the Current Epidemic of Alzheimer's Disease.

    PubMed

    Brewer, George J

    2015-12-02

    It has become clear that copper toxicity is playing a major role in Alzheimer's disease; but why is the brain copper toxicity with cognition loss in Alzheimer's disease so much different clinically than brain copper toxicity in Wilson's disease, which results in a movement disorder? Furthermore, why is the inorganic copper of supplement pills and in drinking water so much more damaging to cognition than the organic copper in food? A recent paper, which shows that almost all food copper is copper-1, that is the copper-2 of foods reverts to the reduced copper-1 form at death or harvest, gives new insight into these questions. The body has an intestinal transport system for copper-1, Ctr1, which channels copper-1 through the liver and into safe channels. Ctr1 cannot absorb copper-2, and some copper-2 bypasses the liver, ends up in the blood quickly, and is toxic to cognition. Humans evolved to handle copper-1 safely, but not copper-2. Alzheimer's is at least in part, a copper-2 toxicity disease, while Wilson's is a general copper overload disease. In this review, we will show that the epidemiology of the Alzheimer's epidemic occurring in developed, but not undeveloped countries, fits with the epidemiology of exposure to copper-2 ingestion leached from copper plumbing and from copper supplement pill ingestion. Increased meat eating in developed countries is also a factor, because it increases copper absorption, and thus over all copper exposure.

  4. Copper-2 Ingestion, Plus Increased Meat Eating Leading to Increased Copper Absorption, Are Major Factors Behind the Current Epidemic of Alzheimer’s Disease

    PubMed Central

    Brewer, George J.

    2015-01-01

    It has become clear that copper toxicity is playing a major role in Alzheimer’s disease; but why is the brain copper toxicity with cognition loss in Alzheimer’s disease so much different clinically than brain copper toxicity in Wilson’s disease, which results in a movement disorder? Furthermore, why is the inorganic copper of supplement pills and in drinking water so much more damaging to cognition than the organic copper in food? A recent paper, which shows that almost all food copper is copper-1, that is the copper-2 of foods reverts to the reduced copper-1 form at death or harvest, gives new insight into these questions. The body has an intestinal transport system for copper-1, Ctr1, which channels copper-1 through the liver and into safe channels. Ctr1 cannot absorb copper-2, and some copper-2 bypasses the liver, ends up in the blood quickly, and is toxic to cognition. Humans evolved to handle copper-1 safely, but not copper-2. Alzheimer’s is at least in part, a copper-2 toxicity disease, while Wilson’s is a general copper overload disease. In this review, we will show that the epidemiology of the Alzheimer’s epidemic occurring in developed, but not undeveloped countries, fits with the epidemiology of exposure to copper-2 ingestion leached from copper plumbing and from copper supplement pill ingestion. Increased meat eating in developed countries is also a factor, because it increases copper absorption, and thus over all copper exposure. PMID:26633489

  5. Process for removing copper in a recoverable form from solid scrap metal

    DOEpatents

    Hartman, Alan D.; Oden, Laurance L.; White, Jack C.

    1995-01-01

    A process for removing copper in a recoverable form from a copper/solid ferrous scrap metal mix is disclosed. The process begins by placing a copper/solid ferrous scrap metal mix into a reactor vessel. The atmosphere within the reactor vessel is purged with an inert gas or oxidizing while the reactor vessel is heated in the area of the copper/solid ferrous scrap metal mix to raise the temperature within the reactor vessel to a selected elevated temperature. Air is introduced into the reactor vessel and thereafter hydrogen chloride is introduced into the reactor vessel to obtain a desired air-hydrogen chloride mix. The air-hydrogen chloride mix is operable to form an oxidizing and chloridizing atmosphere which provides a protective oxide coating on the surface of the solid ferrous scrap metal in the mix and simultaneously oxidizes/chloridizes the copper in the mix to convert the copper to a copper monochloride gas for transport away from the solid ferrous scrap metal. After the copper is completely removed from the copper/solid ferrous scrap metal mix, the flows of air and hydrogen chloride are stopped and the copper monochloride gas is collected for conversion to a recoverable copper species.

  6. Zinc stress induces copper depletion in Acinetobacter baumannii.

    PubMed

    Hassan, Karl A; Pederick, Victoria G; Elbourne, Liam D H; Paulsen, Ian T; Paton, James C; McDevitt, Christopher A; Eijkelkamp, Bart A

    2017-03-11

    The first row transition metal ions zinc and copper are essential to the survival of many organisms, although in excess these ions are associated with significant toxicity. Here, we examined the impact of zinc and copper stress on Acinetobacter baumannii, a common opportunistic pathogen. We show that extracellular zinc stress induces a copper-specific depletion phenotype in A. baumannii ATCC 17978. Supplementation with copper not only fails to rescue this phenotype, but further exacerbates the copper depletion. Extensive analysis of the A. baumannii ATCC 17978 genome identified 13 putative zinc/copper resistance efflux pumps. Transcriptional analyses show that four of these transporters are responsive to zinc stress, five to copper stress and seven to the combination of zinc and copper stress, thereby revealing a likely foundation for the zinc-induced copper starvation in A. baumannii. In addition, we show that zinc and copper play crucial roles in management of oxidative stress and the membrane composition of A. baumannii. Further, we reveal that zinc and copper play distinct roles in macrophage-mediated killing of this pathogen. Collectively, this study supports the targeting of metal ion homeostatic mechanisms as an effective antimicrobial strategy against multi-drug resistant bacterial pathogens.

  7. Influence of water chemistry on the acute toxicity of copper and zinc to the cladoceran Ceriodaphnia cf dubia.

    PubMed

    Hyne, Ross V; Pablo, Fleur; Julli, Moreno; Markich, Scott J

    2005-07-01

    This study determined the influence of key water chemistry parameters (pH, alkalinity, dissolved organic carbon [DOC], and hardness) on the aqueous speciation of copper and zinc and its relationship to the acute toxicity of these metals to the cladoceran Ceriodaphnia cf dubia. Immobilization tests were performed for 48-h in synthetic or natural waters buffered at various pH values from 5.5 to 8.4 (other chemical parameters held constant). The toxicity of copper to C. cf dubia decreased fivefold with increasing pH, whereas the toxicity of zinc increased fivefold with increasing pH. The effect of DOC on copper and zinc toxicity to C. cf dubia was determined using natural fulvic acid in the synthetic water. Increasing DOC was found to decrease linearly the toxicity of copper, with the mean effect concentration of copper that immobilized 50% of the cladocerans (EC50) value 45 times higher at 10 mg/L, relative to 0.1 mg/L DOC at pH 6.5. In contrast, the addition of 10 mg/L DOC only resulted in a very small (1.3-fold) reduction in the toxicity of zinc to C. cf dubia. Copper toxicity to C. cf dubia generally did not vary as a function of hardness, whereas zinc toxicity was reduced by a factor of only two, with an increase in water hardness from 44 to 374 mg CaCO3/L. Increasing bicarbonate alkalinity of synthetic waters (30-125 mg/L as CaCO3) decreased the toxicity of copper up to fivefold, which mainly could be attributed to the formation of copper-carbonate complexes, in addition to a pH effect. The toxicity of copper added to a range of natural waters with varying DOC content, pH, and hardness was consistent with the toxicity predicted using the data obtained from the synthetic waters.

  8. Inhibition of human copper trafficking by a small molecule significantly attenuates cancer cell proliferation.

    PubMed

    Wang, Jing; Luo, Cheng; Shan, Changliang; You, Qiancheng; Lu, Junyan; Elf, Shannon; Zhou, Yu; Wen, Yi; Vinkenborg, Jan L; Fan, Jun; Kang, Heebum; Lin, Ruiting; Han, Dali; Xie, Yuxin; Karpus, Jason; Chen, Shijie; Ouyang, Shisheng; Luan, Chihao; Zhang, Naixia; Ding, Hong; Merkx, Maarten; Liu, Hong; Chen, Jing; Jiang, Hualiang; He, Chuan

    2015-12-01

    Copper is a transition metal that plays critical roles in many life processes. Controlling the cellular concentration and trafficking of copper offers a route to disrupt these processes. Here we report small molecules that inhibit the human copper-trafficking proteins Atox1 and CCS, and so provide a selective approach to disrupt cellular copper transport. The knockdown of Atox1 and CCS or their inhibition leads to a significantly reduced proliferation of cancer cells, but not of normal cells, as well as to attenuated tumour growth in mouse models. We show that blocking copper trafficking induces cellular oxidative stress and reduces levels of cellular ATP. The reduced level of ATP results in activation of the AMP-activated protein kinase that leads to reduced lipogenesis. Both effects contribute to the inhibition of cancer cell proliferation. Our results establish copper chaperones as new targets for future developments in anticancer therapies.

  9. Copper Homeostasis at the Host-Pathogen Interface*

    PubMed Central

    Hodgkinson, Victoria; Petris, Michael J.

    2012-01-01

    The trace element copper is indispensable for all aerobic life forms. Its ability to cycle between two oxidation states, Cu1+ and Cu2+, has been harnessed by a wide array of metalloenzymes that catalyze electron transfer reactions. The metabolic needs for copper are sustained by a complex series of transporters and carrier proteins that regulate its intracellular accumulation and distribution in both pathogenic microbes and their animal hosts. However, copper is also potentially toxic due in part to its ability to generate reactive oxygen species. Recent studies suggest that the macrophage phagosome accumulates copper during bacterial infection, which may constitute an important mechanism of killing. Bacterial countermeasures include the up-regulation of copper export and detoxification genes during infection, which studies suggest are important determinants of virulence. In this minireview, we summarize recent developments that suggest an emerging role for copper as an unexpected component in determining the outcome of host-pathogen interactions. PMID:22389498

  10. Inhibition of human copper trafficking by a small molecule significantly attenuates cancer cell proliferation

    PubMed Central

    Wang, Jing; Luo, Cheng; Shan, Changliang; You, Qiancheng; Lu, Junyan; Elf, Shannon; Zhou, Yu; Wen, Yi; Vinkenborg, Jan L.; Fan, Jun; Kang, Heebum; Lin, Ruiting; Han, Dali; Xie, Yuxin; Karpus, Jason; Chen, Shijie; Ouyang, Shisheng; Luan, Chihao; Zhang, Naixia; Ding, Hong; Merkx, Maarten; Liu, Hong; Chen, Jing; Jiang, Hualiang; He, Chuan

    2016-01-01

    Copper is a transition metal that plays critical roles in many life processes. Controlling the cellular concentration and trafficking of copper offers a route to disrupt these processes. Here we report small molecules that inhibit the human copper-trafficking proteins Atox1 and CCS, and so provide a selective approach to disrupt cellular copper transport. The knockdown of Atox1 and CCS or their inhibition leads to a significantly reduced proliferation of cancer cells, but not of normal cells, as well as to attenuated tumour growth in mouse models. We show that blocking copper trafficking induces cellular oxidative stress and reduces levels of cellular ATP. The reduced level of ATP results in activation of the AMP-activated protein kinase that leads to reduced lipogenesis. Both effects contribute to the inhibition of cancer cell proliferation. Our results establish copper chaperones as new targets for future developments in anticancer therapies. PMID:26587712

  11. Inhibition of human copper trafficking by a small molecule significantly attenuates cancer cell proliferation

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Luo, Cheng; Shan, Changliang; You, Qiancheng; Lu, Junyan; Elf, Shannon; Zhou, Yu; Wen, Yi; Vinkenborg, Jan L.; Fan, Jun; Kang, Heebum; Lin, Ruiting; Han, Dali; Xie, Yuxin; Karpus, Jason; Chen, Shijie; Ouyang, Shisheng; Luan, Chihao; Zhang, Naixia; Ding, Hong; Merkx, Maarten; Liu, Hong; Chen, Jing; Jiang, Hualiang; He, Chuan

    2015-12-01

    Copper is a transition metal that plays critical roles in many life processes. Controlling the cellular concentration and trafficking of copper offers a route to disrupt these processes. Here we report small molecules that inhibit the human copper-trafficking proteins Atox1 and CCS, and so provide a selective approach to disrupt cellular copper transport. The knockdown of Atox1 and CCS or their inhibition leads to a significantly reduced proliferation of cancer cells, but not of normal cells, as well as to attenuated tumour growth in mouse models. We show that blocking copper trafficking induces cellular oxidative stress and reduces levels of cellular ATP. The reduced level of ATP results in activation of the AMP-activated protein kinase that leads to reduced lipogenesis. Both effects contribute to the inhibition of cancer cell proliferation. Our results establish copper chaperones as new targets for future developments in anticancer therapies.

  12. Experimental determinations of soil copper toxicity to lettuce (Lactuca sativa) growth in highly different copper spiked and aged soils.

    PubMed

    Christiansen, Karen S; Borggaard, Ole K; Holm, Peter E; Vijver, Martina G; Hauschild, Michael Z; Peijnenburg, Willie J G M

    2015-04-01

    Accurate knowledge about factors and conditions determining copper (Cu) toxicity in soil is needed for predicting plant growth in various Cu-contaminated soils. Therefore, effects of Cu on growth (biomass production) of lettuce (Lactuca sativa) were tested on seven selected, very different soils spiked with Cu and aged for 2 months at 35 °C. Cu toxicity was expressed as pEC50(Cu(2+)), i.e., the negative logarithm of the EC50(Cu(2+)) activity to plant growth. The determined pEC50(Cu(2+)) was significantly and positively correlated with both the analytically readily available soil pH and concentration of dissolved organic carbon [DOC] which together could explain 87% of the pEC50(Cu(2+)) variation according to the simple equation: pEC50(Cu(2+)) = 0.98 × pH + 345 × [DOC] - 0.27. Other soil characteristics, including the base cation concentrations (Na(+), K(+), Ca(2+), Mg(2+)), the cation exchange capacity at soil pH (ECEC), and at pH 7 (CEC7), soil organic carbon, clay content, and electric conductivity as well as the distribution coefficient (Kd) calculated as the ratio between total soil Cu and water-extractable Cu did not correlate significantly with pEC50(Cu(2+)). Consequently, Cu toxicity, expressed as the negative log of the Cu(2+) activity, to plant growth increases at increasing pH and DOC, which needs to be considered in future management of plant growth on Cu-contaminated soils. The developed regression equation allows identification of soil types in which the phytotoxicity potential of Cu is highest.

  13. 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.

  14. HFE gene mutations and Wilson's disease in Sardinia.

    PubMed

    Sorbello, Orazio; Sini, Margherita; Civolani, Alberto; Demelia, Luigi

    2010-03-01

    Hypocaeruloplasminaemia can lead to tissue iron storage in Wilson's disease and the possibility of iron overload in long-term overtreated patients should be considered. The HFE gene encodes a protein that is intimately involved in intestinal iron absorption. The aim of this study was to determine the prevalence of the HFE gene mutation, its role in iron metabolism of Wilson's disease patients and the interplay of therapy in copper and iron homeostasis. The records of 32 patients with Wilson's disease were reviewed for iron and copper indices, HFE gene mutations and liver biopsy. Twenty-six patients were negative for HFE gene mutations and did not present significant alterations of iron metabolism. The HFE mutation was significantly associated with increased hepatic iron content (P<0.02) and transferrin saturation index (P<0.03). After treatment period, iron indices were significantly decreased only in HFE gene wild-type. The HFE gene mutations may be an addictional factor in iron overload in Wilson's disease. Our results showed that an adjustment of dosage of drugs could prevent further iron overload induced by overtreatment only in patients HFE wild-type. 2009. Published by Elsevier Ltd.

  15. Copper speciation in the gill microenvironment of carp (Cyprinus carpio) at various levels of pH.

    PubMed

    Tao, Shu; Long, Aimin; Xu, Fuliu; Dawson, R W

    2002-07-01

    The fish gill microenvironment of Cyprinus carpio under stress of copper exposure was investigated. pH and other parameters including free copper activity, alkalinity, and inorganic and organic carbons in the surrounding water (inspired water) and in the gill microenvironment (expired water) were measured or calculated at various levels of pH and varying total copper concentrations. The chemical equilibrium calculation (from MINEQA2) and complexation modeling (mucus-copper) were coupled to calculate both species distribution. The results indicate that the pH in the fish gill microenvironment was different from that in the surrounding water with a balance point around 6.9. The secretion of both CO(2) and mucus was affected in both linear and nonlinear ways when the fish were exposed to elevated concentrations of copper. The complexation capacity of the gill mucus was characterized by a conditional stability constant (logk(Cu-mucus)) of 5.37 along with a complexation equivalent concentration (L(Cu-mucus)) of 0.96 mmol Cu/mg C. For both the fish microenvironment and the surrounding water, the dominant copper species shifted from Cu(2+) to CuCO(3)(0) and to Cu(OH)(2)(0) when the pH of the surrounding water changed from 6.12 to 8.11. The change in copper speciation in the gill microenvironment is smaller than that in the surrounding water due to the pH buffering capacity of the fish gills.

  16. 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

  17. Genomic and transcriptomic analyses reveal adaptation mechanisms of an Acidithiobacillus ferrivorans strain YL15 to alpine acid mine drainage.

    PubMed

    Peng, Tangjian; Ma, Liyuan; Feng, Xue; Tao, Jiemeng; Nan, Meihua; Liu, Yuandong; Li, Jiaokun; Shen, Li; Wu, Xueling; Yu, Runlan; Liu, Xueduan; Qiu, Guanzhou; Zeng, Weimin

    2017-01-01

    Acidithiobacillus ferrivorans is an acidophile that often occurs in low temperature acid mine drainage, e.g., that located at high altitude. Being able to inhabit the extreme environment, the bacterium must possess strategies to copy with the survival stress. Nonetheless, information on the strategies is in demand. Here, genomic and transcriptomic assays were performed to illuminate the adaptation mechanisms of an A. ferrivorans strain YL15, to the alpine acid mine drainage environment in Yulong copper mine in southwest China. Genomic analysis revealed that strain has a gene repertoire for metal-resistance, e.g., genes coding for the mer operon and a variety of transporters/efflux proteins, and for low pH adaptation, such as genes for hopanoid-synthesis and the sodium:proton antiporter. Genes for various DNA repair enzymes and synthesis of UV-absorbing mycosporine-like amino acids precursor indicated hypothetical UV radiation-resistance mechanisms in strain YL15. In addition, it has two types of the acquired immune system-type III-B and type I-F CRISPR/Cas modules against invasion of foreign genetic elements. RNA-seq based analysis uncovered that strain YL15 uses a set of mechanisms to adapt to low temperature. Genes involved in protein synthesis, transmembrane transport, energy metabolism and chemotaxis showed increased levels of RNA transcripts. Furthermore, a bacterioferritin Dps gene had higher RNA transcript counts at 6°C, possibly implicated in protecting DNA against oxidative stress at low temperature. The study represents the first to comprehensively unveil the adaptation mechanisms of an acidophilic bacterium to the acid mine drainage in alpine regions.

  18. Genomic and transcriptomic analyses reveal adaptation mechanisms of an Acidithiobacillus ferrivorans strain YL15 to alpine acid mine drainage

    PubMed Central

    Ma, Liyuan; Feng, Xue; Tao, Jiemeng; Nan, Meihua; Liu, Yuandong; Li, Jiaokun; Shen, Li; Wu, Xueling; Yu, Runlan; Liu, Xueduan; Qiu, Guanzhou; Zeng, Weimin

    2017-01-01

    Acidithiobacillus ferrivorans is an acidophile that often occurs in low temperature acid mine drainage, e.g., that located at high altitude. Being able to inhabit the extreme environment, the bacterium must possess strategies to copy with the survival stress. Nonetheless, information on the strategies is in demand. Here, genomic and transcriptomic assays were performed to illuminate the adaptation mechanisms of an A. ferrivorans strain YL15, to the alpine acid mine drainage environment in Yulong copper mine in southwest China. Genomic analysis revealed that strain has a gene repertoire for metal-resistance, e.g., genes coding for the mer operon and a variety of transporters/efflux proteins, and for low pH adaptation, such as genes for hopanoid-synthesis and the sodium:proton antiporter. Genes for various DNA repair enzymes and synthesis of UV-absorbing mycosporine-like amino acids precursor indicated hypothetical UV radiation—resistance mechanisms in strain YL15. In addition, it has two types of the acquired immune system–type III-B and type I-F CRISPR/Cas modules against invasion of foreign genetic elements. RNA-seq based analysis uncovered that strain YL15 uses a set of mechanisms to adapt to low temperature. Genes involved in protein synthesis, transmembrane transport, energy metabolism and chemotaxis showed increased levels of RNA transcripts. Furthermore, a bacterioferritin Dps gene had higher RNA transcript counts at 6°C, possibly implicated in protecting DNA against oxidative stress at low temperature. The study represents the first to comprehensively unveil the adaptation mechanisms of an acidophilic bacterium to the acid mine drainage in alpine regions. PMID:28542527

  19. Relation of serum γ-glutamyl transferase activity with copper in an adult population.

    PubMed

    Peng, You-Fan; Wang, Chun-Fang; Pan, Guo-Gang

    2017-10-26

    The aim of this study was to evaluate the relationship between serum γ-glutamyl transferase (γ-GGT) activity and serum copper in an adult population. We analyzed 281 adult subjects who regularly attended the physical examination center at the Affiliated Hospital of Youjiang Medical University for Nationalities. The demographic and laboratory data of the participants were divided into two groups according to the median of serum γ-GGT activity. Serum copper concentrations in individuals with higher γ-GGT levels were significantly increased compared with those with lower γ-GGT concentrations (9.9±2.41 vs. 11.2±3.36 μmol/L, p<0.001). There was a positive correlation between serum γ-GGT activity and copper in all eligible subjects (r=0.198, p=0.001). Further, serum γ-GGT maintained a positive correlation with serum copper in both males and females (r=0.322, p<0.001; r=0.230, p=0.010). The results of multiple linear regression analysis showed that serum γ-GGT maintained a significantly positive correlation with copper after adjusting for multiple potential confounders (b=0.464, p=0.001). This study suggests that serum γ-GGT activity is correlated with copper in the study population, indicating that serum γ-GGT may be a biomarker to evaluate serum copper levels in an adult population.

  20. Organic solar cells with graphene electrodes and vapor printed poly(3,4-ethylenedioxythiophene) as the hole transporting layers.

    PubMed

    Park, Hyesung; Howden, Rachel M; Barr, Miles C; Bulović, Vladimir; Gleason, Karen; Kong, Jing

    2012-07-24

    For the successful integration of graphene as a transparent conducting electrode in organic solar cells, proper energy level alignment at the interface between the graphene and the adjacent organic layer is critical. The role of a hole transporting layer (HTL) thus becomes more significant due to the generally lower work function of graphene compared to ITO. A commonly used HTL material with ITO anodes is poly(3,4-ethylenedioxythiophene) (PEDOT) with poly(styrenesulfonate) (PSS) as the solid-state dopant. However, graphene's hydrophobic surface renders uniform coverage of PEDOT:PSS (aqueous solution) by spin-casting very challenging. Here, we introduce a novel, yet simple, vapor printing method for creating patterned HTL PEDOT layers directly onto the graphene surface. Vapor printing represents the implementation of shadow masking in combination with oxidative chemical vapor deposition (oCVD). The oCVD method was developed for the formation of blanket (i.e., unpatterened) layers of pure PEDOT (i.e., no PSS) with systematically variable work function. In the unmasked regions, vapor printing produces complete, uniform, smooth layers of pure PEDOT over graphene. Graphene electrodes were synthesized under low-pressure chemical vapor deposition (LPCVD) using a copper catalyst. The use of another electron donor material, tetraphenyldibenzoperiflanthene, instead of copper phthalocyanine in the organic solar cells also improves the power conversion efficiency. With the vapor printed HTL, the devices using graphene electrodes yield comparable performances to the ITO reference devices (η(p,LPCVD) = 3.01%, and η(p,ITO) = 3.20%).

  1. Ecophysiological and metabolic responses to interactive exposure to nutrients and copper excess in the brown macroalga Cystoseira tamariscifolia.

    PubMed

    Celis-Plá, Paula S M; Brown, Murray T; Santillán-Sarmiento, Alex; Korbee, Nathalie; Sáez, Claudio A; Figueroa, Félix L

    2018-03-01

    Global scenarios evidence that contamination due to anthropogenic activities occur at different spatial-temporal scales, being important stressors: eutrophication, due to increased nutrient inputs; and metal pollution, mostly derived from industrial activities. In this study, we investigated ecophysiological and metabolic responses to copper and nutrient excess in the brown macroalga Cystoseira tamariscifolia. Whole plants were incubated in an indoor system under control conditions, two levels of nominal copper (0.5 and 2.0μM), and two levels of nutrient supply for two weeks. Maximal quantum yield (F v /F m ) and maximal electron transport rate (ETR max ) increased under copper exposure. Photosynthetic pigments and phenolic compounds (PC) increased under the highest copper levels. The intra-cellular copper content increased under high copper exposure in both nutrient conditions. C. tamariscifolia from the Atlantic displayed efficient metal exclusion mechanisms, since most of the total copper accumulated by the cell was bound to the cell wall. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. Magnesium and other bivalent cations influence upon sodium montelukast effect in experimental-induced thermoalgesia.

    PubMed

    Nechifor, Mihai; Cuciureanu, Magda; Chelarescu, Dan; Ciubotariu, Diana; Pascu, Mihaela

    2008-03-01

    We tested the influence of magnesium, zinc and copper upon the montelukast (MK, antagonist of cysteinyl leukotriene receptor type 1) effect in experimentally-induced thermoalgesia. We worked on 5 groups of 10 adults, each Wistar rats, that received: group I-control; group II: MK (10 mg/kg) unique administration; group III: MgCl2 (1 mM/kg/day) i.p., 3 days and MK (10 mg/kg) unique administration on the 3rd day; group IV: ZnCl2, (0.1 mM/kg/day), i.p., 3 days and MK (10 mg/kg) unique administration on the 3rd day; group V: copper acetate (0.05 mM/kg/day), i.p., 3 days and MK (10 mg/kg) unique administration on the 3rd day. We determined the thermoalgesic sensitivity (TS) using a tail flick analgesia meter, initially, 3 days after daily cation administration and 3 hours after MK administration. Our data show that MK has a statistically significant reduction of TS vs control group (3.76 +/- 1.04 s vs 1.81 +/- 0.98 s, p < 0.05). Copper and magnesium administration do not significantly change the MK effect to decrease TS. The co-administration of zinc and MK statistically significantly increased the TS of the group that received only MK (2.51 +/- 0.21 s vs 3.76 +/- 1.04 s, p < 0.05). Animals that received only cations (in the above mentioned doses) did not significantly change TS.

  3. The DFT Calculations of Structures and EPR Parameters for the Dinuclear Paddle-Wheel Copper(II) Complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) as Powder or Single Crystal

    NASA Astrophysics Data System (ADS)

    Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua

    2017-10-01

    Density functional theory (DFT) calculations of the structures and the Cu2+ g factors (gx, gy and gz ) and hyperfine coupling tensor A (Ax , Ay and Az ) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

  4. Biosolid colloid-mediated transport of copper, zinc, and lead in waste-amended soils.

    PubMed

    Karathanasis, A D; Johnson, D M C; Matocha, C J

    2005-01-01

    Increasing land applications of biosolid wastes as soil amendments have raised concerns about potential toxic effects of associated metals on the environment. This study investigated the ability of biosolid colloids to transport metals associated with organic waste amendments through subsurface soil environments with leaching experiments involving undisturbed soil monoliths. Biosolid colloids were fractionated from a lime-stabilized, an aerobically digested, and a poultry manure organic waste and applied onto the monoliths at a rate of 0.7 cm/h. Eluents were monitored for Cu, Zn, Pb, and colloid concentrations over 16 to 24 pore volumes of leaching. Mass-balance calculations indicated significantly higher (up to 77 times) metal elutions in association with the biosolid colloids in both total and soluble fractions over the control treatments. Eluted metal loads varied with metal, colloid, and soil type, following the sequences Zn = Cu > Pb, and ADB > PMB > LSB colloids. Colloid and metal elution was enhanced by decreasing pH and colloid size, and increasing soil macroporosity and organic matter content. Breakthrough curves were mostly irregular, showing several maxima and minima as a result of preferential macropore flow and multiple clogging and flushing cycles. Soil- and colloid-metal sorption affinities were not reliable predictors of metal attenuation/elution loads, underscoring the dynamic nature of transport processes. The findings demonstrate the important role of biosolid colloids as contaminant carriers and the significant risk they pose, if unaccounted, for soil and ground water contamination in areas receiving heavy applications of biosolid waste amendments.

  5. Fate and transport of copper-based crop protectants in plasticulture runoff and the impact of sedimentation as a best management practice.

    PubMed

    Gallagher, D L; Johnston, K M; Dietrich, A M

    2001-08-01

    The fate and distribution of copper-based crop protectants, applied to plasticulture tomato fields to protect against disease, were investigated in a greenhouse-scale simulation of farming conditions in a coastal environment. Following rainfall, 99% of the applied copper was found to remain on the fields sorbed to the soil and plants; most of the soil-bound copper was found sorbed to the top 2.5 cm of soil between the plasticulture rows. Of the copper leaving the agricultural fields, 82% was found in the runoff with the majority, 74%. sorbed to the suspended solids. The remaining copper, 18%, leached through the soil and entered the groundwater with 10% in the dissolved phase and 8% sorbed to suspended solids. Although only 1% copper was found to leave the field, this was sufficient to cause high copper concentrations (average 2102+/-433 microg/L total copper and 189+/-139 microg/L dissolved copper) in the runoff. Copper concentrations in groundwater samples were also high (average 312+/-198 microg/L total copper and 216+/-99 microg/L dissolved copper). Sedimentation, a best management practice for reducing copper loadings. was found to reduce the total copper concentrations in runoff by 90% to a concentration of 245+/-127 microg/L; however, dissolved copper concentrations remained stable, averaging 139+/-55 microg/L. Total copper concentrations were significantly reduced by the effective removal of suspended solids with sorbed copper.

  6. Combined zebrafish-yeast chemical-genetic screens reveal gene-copper-nutrition interactions that modulate melanocyte pigmentation.

    PubMed

    Ishizaki, Hironori; Spitzer, Michaela; Wildenhain, Jan; Anastasaki, Corina; Zeng, Zhiqiang; Dolma, Sonam; Shaw, Michael; Madsen, Erik; Gitlin, Jonathan; Marais, Richard; Tyers, Mike; Patton, E Elizabeth

    2010-01-01

    Hypopigmentation is a feature of copper deficiency in humans, as caused by mutation of the copper (Cu(2+)) transporter ATP7A in Menkes disease, or an inability to absorb copper after gastric surgery. However, many causes of copper deficiency are unknown, and genetic polymorphisms might underlie sensitivity to suboptimal environmental copper conditions. Here, we combined phenotypic screens in zebrafish for compounds that affect copper metabolism with yeast chemical-genetic profiles to identify pathways that are sensitive to copper depletion. Yeast chemical-genetic interactions revealed that defects in intracellular trafficking pathways cause sensitivity to low-copper conditions; partial knockdown of the analogous Ap3s1 and Ap1s1 trafficking components in zebrafish sensitized developing melanocytes to hypopigmentation in low-copper environmental conditions. Because trafficking pathways are essential for copper loading into cuproproteins, our results suggest that hypomorphic alleles of trafficking components might underlie sensitivity to reduced-copper nutrient conditions. In addition, we used zebrafish-yeast screening to identify a novel target pathway in copper metabolism for the small-molecule MEK kinase inhibitor U0126. The zebrafish-yeast screening method combines the power of zebrafish as a disease model with facile genome-scale identification of chemical-genetic interactions in yeast to enable the discovery and dissection of complex multigenic interactions in disease-gene networks.

  7. The Intestinal Copper Exporter CUA-1 Is Required for Systemic Copper Homeostasis in Caenorhabditis elegans*♦

    PubMed Central

    Chun, Haarin; Sharma, Anuj Kumar; Lee, Jaekwon; Chan, Jefferson; Jia, Shang; Kim, Byung-Eun

    2017-01-01

    Copper plays key catalytic and regulatory roles in biochemical processes essential for normal growth, development, and health. Defects in copper metabolism cause Menkes and Wilson's disease, myeloneuropathy, and cardiovascular disease and are associated with other pathophysiological states. Consequently, it is critical to understand the mechanisms by which organisms control the acquisition, distribution, and utilization of copper. The intestinal enterocyte is a key regulatory point for copper absorption into the body; however, the mechanisms by which intestinal cells transport copper to maintain organismal copper homeostasis are poorly understood. Here, we identify a mechanism by which organismal copper homeostasis is maintained by intestinal copper exporter trafficking that is coordinated with extraintestinal copper levels in Caenorhabditis elegans. Specifically, we show that CUA-1, the C. elegans homolog of ATP7A/B, localizes to lysosome-like organelles (gut granules) in the intestine under copper overload conditions for copper detoxification, whereas copper deficiency results in a redistribution of CUA-1 to basolateral membranes for copper efflux to peripheral tissues. Worms defective in gut granule biogenesis exhibit defects in copper sequestration and increased susceptibility to toxic copper levels. Interestingly, however, a splice isoform CUA-1.2 that lacks a portion of the N-terminal domain is targeted constitutively to the basolateral membrane irrespective of dietary copper concentration. Our studies establish that CUA-1 is a key intestinal copper exporter and that its trafficking is regulated to maintain systemic copper homeostasis. C. elegans could therefore be exploited as a whole-animal model system to study regulation of intra- and intercellular copper trafficking pathways. PMID:27881675

  8. Neurotoxicity Associated with Platinum-Based Anti-Cancer Agents: What are the Implications of Copper Transporters?

    PubMed

    Stojanovska, Vanesa; McQuade, Rachel; Rybalka, Emma; Nurgali, Kulmira

    2017-01-01

    Platinum-based anti-cancer agents, which include cisplatin, carboplatin and oxaliplatin, are an important class of drugs used in clinical setting to treat a variety of cancers. The cytotoxic efficacy of these drugs is mediated by the formation of inter-strand and intrastrand crosslinks, or platinum adducts on nuclear DNA. There is also evidence demonstrating that mitochondrial DNA is susceptible to platinum-adduct damage in dorsal root ganglia neurons. Although all platinum-based agents form similar DNA adducts, they are quite different in terms of activation, systemic toxicity and tolerance. Platinum-based agents are well known for their neurotoxicity and gastrointestinal side-effects which are major causes for dose limitation and treatment discontinuation compromising the efficacy of anti-cancer treatment. Accumulating evidence in non-neuronal cells shows that the copper transport system is associated with platinum drug sensitivity and resistance. There is minimal research concerning the role of copper transporters within the central and peripheral nervous systems. It is unclear whether neurons are more sensitive to platinum-based drugs, are insufficient in drug clearance, or whether platinum accumulation affects intracellular copper status and coppermediated functions. Understanding these mechanisms is important as neurotoxicity is the predominant side-effect of platinum-based chemotherapy. This review highlights the role of copper transpor ters in drug influx, differences in drug activation and side-effects caused by platinum-based agents, as well as their association with central and peripheral neuropathies and gastrointestinal toxicities. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  9. Corrosion issues in high-level nuclear waste containers

    NASA Astrophysics Data System (ADS)

    Asl, Samin Sharifi

    In this dissertation different aspects of corrosion and electrochemistry of copper, candidate canister material in Scandinavian high-level nuclear waste disposal program, including the thermodynamics and kinetics of the reactions that are predicted to occur in the practical system have been studied. A comprehensive thermodynamic study of copper in contact with granitic groundwater of the type and composition that is expected in the Forsmark repository in Sweden has been performed. Our primary objective was to ascertain whether copper would exist in the thermodynamically immune state in the repository, in which case corrosion could not occur and the issue of corrosion in the assessment of the storage technology would be moot. In spite of the fact that metallic copper has been found to exist for geological times in granitic geological formations, copper is well-known to be activated from the immune state to corrode by specific species that may exist in the environment. The principal activator of copper is known to be sulfur in its various forms, including sulfide (H2S, HS-, S2-), polysulfide (H2Sx, HSx -, Sx 2-), poly sulfur thiosulfate ( SxO3 2-), and polythionates (SxO6 2-). A comprehensive study of this aspect of copper chemistry has never been reported, and yet an understanding of this issue is vital for assessing whether copper is a suitable material for fabricating canisters for the disposal of HLNW. Our study identifies and explores those species that activate copper; these species include sulfur-containing entities as well as other, non-sulfur species that may be present in the repository. The effects of temperature, solution pH, and hydrogen pressure on the kinetics of the hydrogen electrode reaction (HER) on copper in borate buffer solution have been studied by means of steady-state polarization measurements, including electrochemical impedance spectroscopy (EIS). In order to obtain electrokinetic parameters, such as the exchange current density and the cathodic Tafel slope, two stages of optimization have been performed. From the optimization process, the activation energy (Eac) of the HER on copper was obtained as ≈32 kJ mol-1. Moreover, the mechanism of the hydrogen evolution reaction (HER) on copper in mildly alkaline media has been studied by means of EIS over the frequency range of 0.01 Hz ≤ f ≤ 5 kHz. The impedance spectra were modeled using a mechanism based upon the Volmer-Heyrovsky-Tafel steps for hydrogen evolution and by considering the reactions involved in hydrogen atom and hydroxyl group adsorption on the copper surface. A single set of kinetic parameters, including the rate constants and transfer coefficient, have been derived for each pH by optimization of the mechanistic model on the experimental impedance (EIS) data. It is postulated that the HER proceeds through the Volmer-Heyrovsky-Tafel mechanism with the Volmer reaction being the rate-determining step. The kinetics of growth of the passive sulfide film on copper in deaerated aqueous sodium chloride solution as a function of applied potential, sulfide species concentrations and temperature were explored by means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The electronic and compositional properties of the passive layer were investigated with Mott-Schottky analysis and X-ray photoelectron spectroscopy (XPS). It is found that metal vacancies are predominant defects in the barrier layer which is in agreement with the p-type character of the film observed experimentally. A point defect model (PDM) for formation and dissolution of the passive sulfide film on copper is proposed. Finally, the behavior of the system interpreted in terms of reaction mechanisms and kinetic parameters extracted from the experimental impedance data by mathematical optimization using a genetic algorithm approach. The diffusion coefficient of cation vacancies is obtained directly from optimization of the proposed model onto the EIS experimental data and was found to be essentially independent from the applied potential within the passive range. The diffusivity of the predominance defects (cation vacancies) found to increase with increase in solution temperature from approx. 10-13 (cm2 s-1 ) at 25 °C to 10-11 (cm2 S -1) at 75 °C.

  10. Recombination activity of light-activated copper defects in p-type silicon studied by injection- and temperature-dependent lifetime spectroscopy

    NASA Astrophysics Data System (ADS)

    Inglese, Alessandro; Lindroos, Jeanette; Vahlman, Henri; Savin, Hele

    2016-09-01

    The presence of copper contamination is known to cause strong light-induced degradation (Cu-LID) in silicon. In this paper, we parametrize the recombination activity of light-activated copper defects in terms of Shockley—Read—Hall recombination statistics through injection- and temperature dependent lifetime spectroscopy (TDLS) performed on deliberately contaminated float zone silicon wafers. We obtain an accurate fit of the experimental data via two non-interacting energy levels, i.e., a deep recombination center featuring an energy level at Ec-Et=0.48 -0.62 eV with a moderate donor-like capture asymmetry ( k =1.7 -2.6 ) and an additional shallow energy state located at Ec-Et=0.1 -0.2 eV , which mostly affects the carrier lifetime only at high-injection conditions. Besides confirming these defect parameters, TDLS measurements also indicate a power-law temperature dependence of the capture cross sections associated with the deep energy state. Eventually, we compare these results with the available literature data, and we find that the formation of copper precipitates is the probable root cause behind Cu-LID.

  11. A morphological study of the sulfurisation of digenite to covellite using reflected polarised light microscopy

    NASA Astrophysics Data System (ADS)

    Rask Møller Frøkiær, Heidi; Warner, Terence E.

    2017-08-01

    A series of copper rods were reacted with sulfur vapour in evacuated glass ampoules at ∼445 °C. Product materials were characterised by powder X-ray diffraction and reflected polarised light microscopy. Copper sulfurised rapidly to digenite, γ-Cu2-xS, under these conditions, whereas the subsequent sulfurisation to covellite, CuS, was notably slower, yielding texturally distinguishable inner (secondary) and outer (primary) CuS regions. A two-stage partial sulfurisation of γ-Cu1.8S resulted in the external growth of two successive layers of primary CuS, which demonstrates decisively that covellite - besides being a p-type metal - is ionically conducting at 445 °C, although considerably less so than digenite. We infer that the growth of platy covellite crystals and their radial alignment in the primary CuS layer are a consequence of copper ion mobility being restricted to the basal plane of the covellite structure. Sulfurising a coil of copper wire at ∼445 °C is an effective method for synthesising covellite.

  12. Interaction of atomic oxygen with thin film and bulk copper: An XPS, AES, XRD, and profilometer study

    NASA Technical Reports Server (NTRS)

    Raikar, Genesh N.; Gregory, John C.; Christl, Ligia C.; Peters, Palmer N.

    1992-01-01

    The University of Alabama in Huntsville (UAH) experiment A-0114 was designed primarily to study degradation of material surfaces due to low earth orbital (LEO) atmospheric oxygen. The experiment contained 128 one inch circular samples: metals, polymers, carbons, and semiconductors. Among metal samples, copper has shown some interesting new results. Two types of copper samples, a film sputter coated on fused silica and a bulk piece of OFHC copper, were characterized employing a variety of techniques such as X-ray and Auger electron spectroscopies, X-ray diffraction, and high resolution profilometry. Cu 2p core level spectra were used to characterize the presence of Cu2O and CuO in addition to Cu Auger LMM lines. These results are supported by our recent X-ray diffraction studies which clearly establish the presence of Cu oxides which we were unable to prove in our earlier work. Profilometry showed an increase in thickness of the film sample where exposed to 106.7 +/- 0.5 nm from an initial thickness of 74.2 +/- 1.1 nm. Further studies with SEM and ellipsometry are underway.

  13. 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.

  14. 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

  15. Photosynthetic Electron Transport Chain of Chlamydomonas reinhardi. IV. Purification and Properties of Plastocyanin.

    PubMed

    Gorman, D S; Levine, R P

    1966-12-01

    The copper protein plastocyanin has been found to be an essential component of the photosynthetic electron transport chain of Chlamydomonas reinhardi, and in this paper we describe a method for its isolation and purification from the wild-type strain. In addition, we describe some of its properties and compare them with those reported for spinach plastocyanin.The plastocyanin was extracted from acetone powders prepared from intact cells, and it was purified by ion exchange chromatography on DEAE cellulose and gel filtration on Sephadex G-75. The yield of the purified protein ranged from plastocyanin equivalent to 2.0 to 2.5 mug atoms copper per 1000 mumoles chlorophyll. In general the absorption spectrum of plastocyanin from C. reinhardi resembled that of the plastocyanin from spinach. Some spectral differences were found in the ultraviolet region where, in contrast to spinach plastocyanin, that of C. reinhardi had a greater absorbance (relative to peaks in the visible) and less evidence for phenylalanine fine structure. The normal oxidation-reduction potential of C. reinhardi plastocyanin was found to be + 0.37 volts, the same as reported for spinach plastocyanin. The molecular weight of C. reinhardi plastocyanin has been estimated to be 13,000 +/- 2000. In contrast, the value for spinach plastocyanin has been found to be 21,000.

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

    PubMed

    Zhang, Hong; Andrews, Susan A

    2012-05-15

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

  17. Detection of Genetically Altered Copper Levels in Drosophila Tissues by Synchrotron X-Ray Fluorescence Microscopy

    PubMed Central

    Lye, Jessica C.; Hwang, Joab E. C.; Paterson, David; de Jonge, Martin D.; Howard, Daryl L.; Burke, Richard

    2011-01-01

    Tissue-specific manipulation of known copper transport genes in Drosophila tissues results in phenotypes that are presumably due to an alteration in copper levels in the targeted cells. However direct confirmation of this has to date been technically challenging. Measures of cellular copper content such as expression levels of copper-responsive genes or cuproenzyme activity levels, while useful, are indirect. First-generation copper-sensitive fluorophores show promise but currently lack the sensitivity required to detect subtle changes in copper levels. Moreover such techniques do not provide information regarding other relevant biometals such as zinc or iron. Traditional techniques for measuring elemental composition such as inductively coupled plasma mass spectroscopy are not sensitive enough for use with the small tissue amounts available in Drosophila research. Here we present synchrotron x-ray fluorescence microscopy analysis of two different Drosophila tissues, the larval wing imaginal disc, and sectioned adult fly heads and show that this technique can be used to detect changes in tissue copper levels caused by targeted manipulation of known copper homeostasis genes. PMID:22053217

  18. Effect of baicalin-copper on the induction of apoptosis in human hepatoblastoma cancer HepG2 cells.

    PubMed

    Li, Xiaoli; Zou, Kaili; Gou, Jing; Du, Qin; Li, Dejuan; He, Xiaoyan; Li, Zhubo

    2015-03-01

    The medical properties of baicalin have been well known for many years. However, the discovery that baicalin in the presence of metal ions is more effective than baicalin alone changed the course of drug research. The present study was designed to investigate the effect and possible mechanism of apoptosis induced by baicalin-copper in a human hepatoblastoma cancer cell line (HepG2) and in vivo. This study demonstrated that baicalin-copper suppresses the proliferation of HepG2 cells in a dose-dependent manner. Intraperitoneal injection of baicalin-copper resulted in a significant decrease in tumor growth in xenografts in nude mice. Acridine orange staining and flow cytometry analysis demonstrated that baicalin-copper induced apoptosis in HepG2 cells and caused cells to arrest in G2-M phase of the cell cycle. Furthermore, baicalin-copper treatment significantly increased the Bax/Bcl-2 ratio and p38 levels, as well as decreased the expression of caspase-3, p-PI3K, p-Akt and p-mTOR (P < 0.01). All of the evidences above indicate that baicalin-copper induces apoptosis in HepG2 cells by down-regulating the PI3K/Akt/mTOR signaling pathway.

  19. Comprehensive comparison of two protein family of P-ATPases (13A1 and 13A3) in insects.

    PubMed

    Seddigh, Samin

    2017-06-01

    The P-type ATPases (P-ATPases) are present in all living cells where they mediate ion transport across membranes on the expense of ATP hydrolysis. Different ions which are transported by these pumps are protons like calcium, sodium, potassium, and heavy metals such as manganese, iron, copper, and zinc. Maintenance of the proper gradients for essential ions across cellular membranes makes P-ATPases crucial for cell survival. In this study, characterization of two families of P-ATPases including P-ATPase 13A1 and P-ATPase 13A3 protein was compared in two different insect species from different orders. According to the conserved motifs found with MEME, nine motifs were shared by insects of 13A1 family but eight in 13A3 family. Seven different insect species from 13A1 and five samples from 13A3 family were selected as the representative samples for functional and structural analyses. The structural and functional analyses were performed with ProtParam, SOPMA, SignalP 4.1, TMHMM 2.0, ProtScale and ProDom tools in the ExPASy database. The tertiary structure of Bombus terrestris as a sample of each family of insects were predicted by the Phyre2 and TM-score servers and their similarities were verified by SuperPose server. The tertiary structures were predicted via the "c3b9bA" model (PDB Accession Code: 3B9B) in P-ATPase 13A1 family and "c2zxeA" model (PDB Accession Code: 2ZXE) in P-ATPase 13A3 family. A phylogenetic tree was constructed with MEGA 6.06 software using the Neighbor-joining method. According to the results, there was a high identity of P-ATPase families so that they should be derived from a common ancestor however they belonged to separate groups. In protein-protein interaction analysis by STRING 10.0, six common enriched pathways of KEGG were identified in B. terrestris in both families. The obtained data provide a background for bioinformatic studies of the function and evolution of other insects and organisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. 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

  1. Effects of RF plasma treatment on spray-pyrolyzed copper oxide films on silicon substrates

    NASA Astrophysics Data System (ADS)

    Madera, Rozen Grace B.; Martinez, Melanie M.; Vasquez, Magdaleno R., Jr.

    2018-01-01

    The effects of radio-frequency (RF) argon (Ar) plasma treatment on the structural, morphological, electrical and compositional properties of the spray-pyrolyzed p-type copper oxide films on n-type (100) silicon (Si) substrates were investigated. The films were successfully synthesized using 0.3 M copper acetate monohydrate sprayed on precut Si substrates maintained at 350 °C. X-ray diffraction revealed cupric oxide (CuO) with a monoclinic structure. An apparent improvement in crystallinity was realized after Ar plasma treatment, attributed to the removal of residues contaminating the surface. Scanning electron microscope images showed agglomerated monoclinic grains and revealed a reduction in size upon plasma exposure induced by the sputtering effect. The current-voltage characteristics of CuO/Si showed a rectifying behavior after Ar plasma exposure with an increase in turn-on voltage. Four-point probe measurements revealed a decrease in sheet resistance after plasma irradiation. Fourier transform infrared spectral analyses also showed O-H and C-O bands on the films. This work was able to produce CuO thin films via spray pyrolysis on Si substrates and enhancement in their properties by applying postdeposition Ar plasma treatment.

  2. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

  4. [Copper intake and blood levels as risk factors for atheromatous disease].

    PubMed

    Albala, C; Salazar, G; Vío, F; Araya, F; Feuerhacke, W; Olivares, S; Alvarez, G

    1997-08-01

    Copper is part of antioxidant enzymes and could have a cardiovascular protective effect. A higher cardiovascular risk has been associated with high as well as low plasma copper levels. To search for differences in copper intake and plasma levels between patients with coronary artery or cerebrovascular diseases and normal subjects. Zinc and copper intake, plasma levels and serum lipid levels were measured in 20 patients with cerebrovascular disease, 20 patients with an acute myocardial infarction and 40 subjects hospitalized for elective surgery, that served as controls. Copper and zinc intake was below recommended allowances in all subjects. Serum zinc and copper levels did not differ in the three study groups. In patients with myocardial infarction a weak correlation was found between serum copper and total cholesterol (r = 0.24; p < 0.05) and LDL cholesterol (r = 0.31; p < 0.05). No differences in copper levels were found in subjects with atherosclerosis and controls. The correlation between serum copper and cholesterol deserves further investigation.

  5. Understanding and control of bipolar self-doping in copper nitride

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

    Fioretti, Angela N., E-mail: afiorett@mines.edu, E-mail: riy.zakutayev@nrel.gov; Tamboli, Adele C.; Caskey, Christopher M.

    2016-05-14

    Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu{sub 3}N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu{sub 3}N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu{sub 3}N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu{sub 3}N with 10{sup 17} electrons/cm{sup 3}more » for low growth temperature (≈35 °C) and p-type with 10{sup 15} holes/cm{sup 3}–10{sup 16} holes/cm{sup 3} for elevated growth temperatures (50 °C–120 °C). Mobility for both types of Cu{sub 3}N was ≈0.1 cm{sup 2}/Vs–1 cm{sup 2}/Vs. Additionally, temperature-dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that V{sub Cu} defects form preferentially in p-type Cu{sub 3}N, while Cu{sub i} defects form preferentially in n-type Cu{sub 3}N, suggesting that Cu{sub 3}N is a compensated semiconductor with conductivity type resulting from a balance between donor and acceptor defects. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu{sub 3}N that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials and provide a framework that can be applied when considering the properties of such materials in general.« less

  6. Diverse Functional Properties of Wilson Disease ATP7B Variants

    PubMed Central

    Huster, Dominik; Kühne, Angelika; Bhattacharjee, Ashima; Raines, Lily; Jantsch, Vanessa; Noe, Johannes; Schirrmeister, Wiebke; Sommerer, Ines; Sabri, Osama; Berr, Frieder; Mössner, Joachim; Stieger, Bruno; Caca, Karel; Lutsenko, Svetlana

    2012-01-01

    BACKGROUND & AIMS Wilson disease is a severe disorder of copper metabolism caused by mutations in ATP7B, which encodes a copper-transporting adenosine triphosphatase. The disease presents with a variable phenotype that complicates the diagnostic process and treatment. Little is known about the mechanisms that contribute to the different phenotypes of the disease. METHODS We analyzed 28 variants of ATP7B from patients with Wilson disease that affected different functional domains; the gene products were expressed using the baculovirus expression system in Sf9 cells. Protein function was analyzed by measuring catalytic activity and copper (64Cu) transport into vesicles. We studied intracellular localization of variants of ATP7B that had measurable transport activities and were tagged with green fluorescent protein in mammalian cells using confocal laser scanning microscopy. RESULTS Properties of ATP7B variants with pathogenic amino-acid substitution varied greatly even if substitutions were in the same functional domain. Some variants had complete loss of catalytic and transport activity, whereas others lost transport activity but retained phosphor-intermediate formation or had partial losses of activity. In mammalian cells, transport-competent variants differed in stability and subcellular localization. CONCLUSIONS Variants in ATP7B associated with Wilson disease disrupt the protein’s transport activity, result in its mislocalization, and reduce its stability. Single assays are insufficient to accurately predict the effects of ATP7B variants the function of its product and development of Wilson disease. These findings will contribute to our understanding of genotype–phenotype correlation and mechanisms of disease pathogenesis. PMID:22240481

  7. 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.

  8. Evolution and diversity of periplasmic proteins involved in copper homeostasis in gamma proteobacteria

    PubMed Central

    2012-01-01

    Background Different systems contributing to copper homeostasis in bacteria have been described in recent years involving periplasmic and transport proteins that provide resistance via metal efflux to the extracellular media (CopA/Cue, Cus, Cut, and Pco). The participation of these proteins in the assembly of membrane, periplasmic and secreted cuproproteins has also been postulated. The integration and interrelation of these systems and their apparent redundancies are less clear since they have been studied in alternative systems. Based on the idea that cellular copper is not free but rather it is transferred via protein-protein interactions, we hypothesized that systems would coevolve and be constituted by set numbers of essential components. Results By the use of a phylogenomic approach we identified the distribution of 14 proteins previously characterized as members of homeostasis systems in the genomes of 268 gamma proteobacteria. Only 3% of the genomes presented the complete systems and 5% of them, all intracellular parasites, lacked the 14 genes. Surprisingly, copper homeostatic pathways did not behave as evolutionary units with particular species assembling different combinations of basic functions. The most frequent functions, and probably because of its distribution the most vital, were copper extrusion from the cytoplasm to the periplasm performed by CopA and copper export from the cytoplasm to the extracellular space performed by CusC, which along with the remaining 12 proteins, assemble in nine different functional repertoires. Conclusions These observations suggest complex evolutionary dynamics and still unexplored interactions to achieve copper homeostasis, challenging some of the molecular transport mechanism proposed for these systems. PMID:23122209

  9. The Activity of Menkes Disease Protein ATP7A Is Essential for Redox Balance in Mitochondria.

    PubMed

    Bhattacharjee, Ashima; Yang, Haojun; Duffy, Megan; Robinson, Emily; Conrad-Antoville, Arianrhod; Lu, Ya-Wen; Capps, Tony; Braiterman, Lelita; Wolfgang, Michael; Murphy, Michael P; Yi, Ling; Kaler, Stephen G; Lutsenko, Svetlana; Ralle, Martina

    2016-08-05

    Copper-transporting ATPase ATP7A is essential for mammalian copper homeostasis. Loss of ATP7A activity is associated with fatal Menkes disease and various other pathologies. In cells, ATP7A inactivation disrupts copper transport from the cytosol into the secretory pathway. Using fibroblasts from Menkes disease patients and mouse 3T3-L1 cells with a CRISPR/Cas9-inactivated ATP7A, we demonstrate that ATP7A dysfunction is also damaging to mitochondrial redox balance. In these cells, copper accumulates in nuclei, cytosol, and mitochondria, causing distinct changes in their redox environment. Quantitative imaging of live cells using GRX1-roGFP2 and HyPer sensors reveals highest glutathione oxidation and elevation of H2O2 in mitochondria, whereas the redox environment of nuclei and the cytosol is much less affected. Decreasing the H2O2 levels in mitochondria with MitoQ does not prevent glutathione oxidation; i.e. elevated copper and not H2O2 is a primary cause of glutathione oxidation. Redox misbalance does not significantly affect mitochondrion morphology or the activity of respiratory complex IV but markedly increases cell sensitivity to even mild glutathione depletion, resulting in loss of cell viability. Thus, ATP7A activity protects mitochondria from excessive copper entry, which is deleterious to redox buffers. Mitochondrial redox misbalance could significantly contribute to pathologies associated with ATP7A inactivation in tissues with paradoxical accumulation of copper (i.e. renal epithelia). © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  10. The Activity of Menkes Disease Protein ATP7A Is Essential for Redox Balance in Mitochondria

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

    Bhattacharjee, Ashima; Yang, Haojun; Duffy, Megan

    Copper-transporting ATPase ATP7A is essential for mammalian copper homeostasis. Loss of ATP7A activity is associated with fatal Menkes disease and various other pathologies. In cells, ATP7A inactivation disrupts copper transport from the cytosol into the secretory pathway. Using fibroblasts from Menkes disease patients and mouse 3T3-L1 cells with a CRISPR/Cas9-inactivated ATP7A, we demonstrate that ATP7A dysfunction is also damaging to mitochondrial redox balance. In these cells, copper accumulates in nuclei, cytosol, and mitochondria, causing distinct changes in their redox environment. Quantitative imaging of live cells using GRX1-roGFP2 and HyPer sensors reveals highest glutathione oxidation and elevation of H2O2 in mitochondria,more » whereas the redox environment of nuclei and the cytosol is much less affected. Decreasing the H2O2 levels in mitochondria with MitoQ does not prevent glutathione oxidation; i.e. elevated copper and not H2O2 is a primary cause of glutathione oxidation. Redox misbalance does not significantly affect mitochondrion morphology or the activity of respiratory complex IV but markedly increases cell sensitivity to even mild glutathione depletion, resulting in loss of cell viability. Thus, ATP7A activity protects mitochondria from excessive copper entry, which is deleterious to redox buffers. Mitochondrial redox misbalance could significantly contribute to pathologies associated with ATP7A inactivation in tissues with paradoxical accumulation of copper (i.e. renal epithelia).« less

  11. The Activity of Menkes Disease Protein ATP7A Is Essential for Redox Balance in Mitochondria*

    PubMed Central

    Bhattacharjee, Ashima; Yang, Haojun; Duffy, Megan; Robinson, Emily; Conrad-Antoville, Arianrhod; Lu, Ya-Wen; Capps, Tony; Braiterman, Lelita; Wolfgang, Michael; Murphy, Michael P.; Yi, Ling; Kaler, Stephen G.; Lutsenko, Svetlana; Ralle, Martina

    2016-01-01

    Copper-transporting ATPase ATP7A is essential for mammalian copper homeostasis. Loss of ATP7A activity is associated with fatal Menkes disease and various other pathologies. In cells, ATP7A inactivation disrupts copper transport from the cytosol into the secretory pathway. Using fibroblasts from Menkes disease patients and mouse 3T3-L1 cells with a CRISPR/Cas9-inactivated ATP7A, we demonstrate that ATP7A dysfunction is also damaging to mitochondrial redox balance. In these cells, copper accumulates in nuclei, cytosol, and mitochondria, causing distinct changes in their redox environment. Quantitative imaging of live cells using GRX1-roGFP2 and HyPer sensors reveals highest glutathione oxidation and elevation of H2O2 in mitochondria, whereas the redox environment of nuclei and the cytosol is much less affected. Decreasing the H2O2 levels in mitochondria with MitoQ does not prevent glutathione oxidation; i.e. elevated copper and not H2O2 is a primary cause of glutathione oxidation. Redox misbalance does not significantly affect mitochondrion morphology or the activity of respiratory complex IV but markedly increases cell sensitivity to even mild glutathione depletion, resulting in loss of cell viability. Thus, ATP7A activity protects mitochondria from excessive copper entry, which is deleterious to redox buffers. Mitochondrial redox misbalance could significantly contribute to pathologies associated with ATP7A inactivation in tissues with paradoxical accumulation of copper (i.e. renal epithelia). PMID:27226607

  12. Geochemical Exploration Techniques Applicable in the Search for Copper Deposits

    USGS Publications Warehouse

    Chaffee, Maurice A.

    1975-01-01

    Geochemical exploration is an important part of copper-resource evaluation. A large number of geochemical exploration techniques, both proved and untried, are available to the geochemist to use in the search for new copper deposits. Analyses of whole-rock samples have been used in both regional and local geochemical exploration surveys in the search for copper. Analyses of mineral separates, such as biotite, magnetite, and sulfides, have also been used. Analyses of soil samples are widely used in geochemical exploration, especially for localized surveys. It is important to distinguish between residual and transported soil types. Orientation studies should always be conducted prior to a geochemical investigation in a given area in order to determine the best soil horizon and the best size of soil material for sampling in that area. Silty frost boils, caliche, and desert varnish are specialized types of soil samples that might be useful sampling media. Soil gas is a new and potentially valuable geochemical sampling medium, especially in exploring for buried mineral deposits in arid regions. Gaseous products in samples of soil may be related to base-metal deposits and include mercury vapor, sulfur dioxide, hydrogen sulfide, carbon oxysulfide, carbon dioxide, hydrogen, oxygen, nitrogen, the noble gases, the halogens, and many hydrocarbon compounds. Transported materials that have been used in geochemical sampling programs include glacial float boulders, glacial till, esker gravels, stream sediments, stream-sediment concentrates, and lake sediments. Stream-sediment sampling is probably the most widely used and most successful geochemical exploration technique. Hydrogeochemical exploration programs have utilized hot- and cold-spring waters and their precipitates as well as waters from lakes, streams, and wells. Organic gel found in lakes and at stream mouths is an unproved sampling medium. Suspended material and dissolved gases in any type of water may also be useful media. Samples of ice and snow have been used for limited geochemical surveys. Both geobotanical and biogeochemical surveys have been successful in locating copper deposits in many parts of the world. Micro-organisms, including bacteria and algae, are other unproved media that should be studied. Animals can be used in geochemical-prospecting programs. Dogs have been used quite successfully to sniff out hidden and exposed sulfide minerals. Tennite mounds are commonly composed of subsurface material, but have not as yet proved to be useful in locating buried mineral deposits. Animal tissue and waste products are essentially unproved but potentially valuable sampling media. Knowledge of the location of areas where trace-element-associated diseases in animals and man are endemic as well as a better understanding of these diseases, may aid in identifying regions that are enriched in or depleted of various elements, including copper. Results of analyses of gases in the atmosphere are proving valuable in mineral-exploration surveys. Studies involving metallic compounds exhaled by plants into the atmosphere, and of particulate matter suspended in the atmosphere are reviewed these methods may become important in the future. Remote-sensing techniques are useful for making indirect measurements of geochemical responses. Two techniques applicable to geochemical exploration are neutron-activation analysis and gamma-ray spectrometry. Aerial photography is especially useful in vegetation surveys. Radar imagery is an unproved but potentially valuable method for use in studies of vegetation in perpetually clouded regions. With the advent of modern computers, many new techniques, such as correlation analysis, regression analysis, discriminant analysis, factor analysis, cluster analysis, trend-surface analysis, and moving-average analysis can be applied to geochemical data sets. Selective use of these techniques can provide new insights into the interpretatio

  13. Alloy Development, Processing and Characterization of Devitrified Titanium Base Microcrystalline Alloys.

    DTIC Science & Technology

    1984-12-01

    quench rates (10V 10V [/sec). Since the heat transport and temperature profile of Ti melt in the cold copper crucible are not well known, melting...experiments in a cold copper crucible by arc heating were conducted using Ti-6.3Si alloy. The temperature measurement at both the surface and the bottom of the...melt spinning compart- ment B, and ribbon processing chamber C. The pre-melted alloy ingot is . - " charged directly into a cold copper crucible while

  14. Development of a selective and sensitive flotation method for determination of trace amounts of cobalt, nickel, copper and iron in environmental samples.

    PubMed

    Karimi, H; Ghaedi, M; Shokrollahi, A; Rajabi, H R; Soylak, M; Karami, B

    2008-02-28

    A simple, selective and rapid flotation method for the separation-preconcentration of trace amounts of cobalt, nickel, iron and copper ions using phenyl 2-pyridyl ketone oxime (PPKO) has been developed prior to their flame atomic absorption spectrometric determinations. The influence of pH, amount of PPKO as collector, type and amount of eluting agent, type and amount of surfactant as floating agent and ionic strength was evaluated on the recoveries of analytes. The influences of the concomitant ions on the recoveries of the analyte ions were also examined. The enrichment factor was 93. The detection limits based on 3 sigma for Cu, Ni, Co and Fe were 0.7, 0.7, 0.8, and 0.7 ng mL(-1), respectively. The method has been successfully applied for determination of trace amounts of ions in various real samples.

  15. Copper-resistant bacteria reduces oxidative stress and uptake of copper in lentil plants: potential for bacterial bioremediation.

    PubMed

    Islam, Faisal; Yasmeen, Tahira; Ali, Qasim; Mubin, Muhammad; Ali, Shafaqat; Arif, Muhammad Saleem; Hussain, Sabir; Riaz, Muhammad; Abbas, Farhat

    2016-01-01

    For effective microbe-assisted bioremediation, metal-resistant plant growth-promoting bacteria (PGPB) must facilitate plant growth by restricting excess metal uptake in plants, leading to prevent its bio-amplification in the ecosystem. The aims of our study were to isolate and characterize copper (Cu)-resistant PGPB from waste water receiving contaminated soil. In addition, we investigated the phytotoxic effect of copper on the lentil plants inoculated with copper-resistant bacteria Providencia vermicola, grown in copper-contaminated soil. Copper-resistant P. vermicola showed multiple plant growth promoting characteristics, when used as a seed inoculant. It protected the lentil plants from copper toxicity with a considerable increase in root and shoot length, plant dry weight and leaf area. A notable increase in different gas exchange characteristics such as A, E, C i , g s , and A/E, as well as increase in N and P accumulation were also recorded in inoculated plants as compared to un-inoculated copper stressed plants. In addition, leaf chlorophyll content, root nodulation, number of pods, 1,000 seed weight were also higher in inoculated plants as compared with non-inoculated ones. Anti-oxidative defense mechanism improved significantly via elevated expression of reactive oxygen species -scavenging enzymes including ascorbate peroxidase, superoxide dismutase, catalase, and guaiacol peroxidase with alternate decrease in malondialdehyde and H2O2 contents, reduced electrolyte leakage, proline, and total phenolic contents suggesting that inoculation of P. vermicola triggered heavy metals stress-related defense pathways under copper stress. Overall, the results demonstrated that the P. vermicola seed inoculation confer heavy metal stress tolerance in lentil plant which can be used as a potent biotechnological tool to cope with the problems of copper pollution in crop plants for better yield.

  16. Transcriptomic and metabolomic analysis of copper stress acclimation in Ectocarpus siliculosus highlights signaling and tolerance mechanisms in brown algae

    PubMed Central

    2014-01-01

    Background Brown algae are sessile macro-organisms of great ecological relevance in coastal ecosystems. They evolved independently from land plants and other multicellular lineages, and therefore hold several original ontogenic and metabolic features. Most brown algae grow along the coastal zone where they face frequent environmental changes, including exposure to toxic levels of heavy metals such as copper (Cu). Results We carried out large-scale transcriptomic and metabolomic analyses to decipher the short-term acclimation of the brown algal model E. siliculosus to Cu stress, and compared these data to results known for other abiotic stressors. This comparison demonstrates that Cu induces oxidative stress in E. siliculosus as illustrated by the transcriptomic overlap between Cu and H2O2 treatments. The common response to Cu and H2O2 consisted in the activation of the oxylipin and the repression of inositol signaling pathways, together with the regulation of genes coding for several transcription-associated proteins. Concomitantly, Cu stress specifically activated a set of genes coding for orthologs of ABC transporters, a P1B-type ATPase, ROS detoxification systems such as a vanadium-dependent bromoperoxidase, and induced an increase of free fatty acid contents. Finally we observed, as a common abiotic stress mechanism, the activation of autophagic processes on one hand and the repression of genes involved in nitrogen assimilation on the other hand. Conclusions Comparisons with data from green plants indicate that some processes involved in Cu and oxidative stress response are conserved across these two distant lineages. At the same time the high number of yet uncharacterized brown alga-specific genes induced in response to copper stress underlines the potential to discover new components and molecular interactions unique to these organisms. Of particular interest for future research is the potential cross-talk between reactive oxygen species (ROS)-, myo-inositol-, and oxylipin signaling. PMID:24885189

  17. Porous silicon-copper phthalocyanine heterostructure based photoelectrochemical cell

    NASA Astrophysics Data System (ADS)

    A. Betty, C.; N, Padma; Arora, Shalav; Survaiya, Parth; Bhattacharya, Debarati; Choudhury, Sipra; Roy, Mainak

    2018-01-01

    A hybrid solar cell consisting of nanostructured p-type porous silicon (PS) deposited with visible light absorbing dye, Copper Phthalocyanine (CuPc) has been prepared in the photoelectrochemical cell configuration. P-type PS with (100) and (111) orientations which have different porous structures were used for studying the effects of the substrate morphology on the cell efficiency. Heterostructures were prepared by depositing three different thicknesses of CuPc for optimizing the cell efficiency. Structural and surface characterizations were studied using XRD, Raman, SEM and AFM on the PS-CuPc heterostructure. XRD spectrum on both plane silicon and porous silicon indicates the π-π stacking of CuPc with increased disorder for CuPc film on porous silicon. Electrochemical characterizations under sun light type radiation have been carried out to evaluate the photosensitivity of the heterostructure. Between the two different substrates, (100) PS gives better photocurrent, possibly due to the higher surface area and lower series resistance of the structure. Among the (100) PS substrates, (100) PS with 15 nm CuPc film gives Voc more than 1 V resulting in higher efficiency for the cell. The study suggests the scope for optimization of solar cell efficiency using various combinations of the substrate structure and thickness of the sensitizing layer.

  18. Efficient organic solar cells using copper(I) iodide (CuI) hole transport layers

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

    Peng, Ying; Department of Physics and Centre for Plastic Electronics, Blackett Laboratory, Imperial College London, London SW7 2AZ; Yaacobi-Gross, Nir

    We report the fabrication of high power conversion efficiency (PCE) polymer/fullerene bulk heterojunction (BHJ) photovoltaic cells using solution-processed Copper (I) Iodide (CuI) as hole transport layer (HTL). Our devices exhibit a PCE value of ∼5.5% which is equivalent to that obtained for control devices based on the commonly used conductive polymer poly(3,4-ethylenedioxythiophene): polystyrenesulfonate as HTL. Inverted cells with PCE >3% were also demonstrated using solution-processed metal oxide electron transport layers, with a CuI HTL evaporated on top of the BHJ. The high optical transparency and suitable energetics of CuI make it attractive for application in a range of inexpensive large-area optoelectronicmore » devices.« less

  19. Biochemical Evolution of Iron and Copper Proteins, Substances Vital to Life

    ERIC Educational Resources Information Center

    Frieden, Earl

    1974-01-01

    Summarizes studies in the area of biochemical evolution of iron, copper, and heme proteins to provide an historical outline. Included are lists of major kinds of proteins and enzymes and charts illustrating electron flow in a cytochrome electron transport system and interconversion of jerrous to ferric ion in iron metabolism. (CC)

  20. Early-Stage Research & Development | Transportation Research | NREL

    Science.gov Websites

    thermal conductivity of packed copper wire used in electric-drive vehicle motor applications provides a research on thermal management in copper-wound electric motors is helping to improve the performance and reliability of electric-drive vehicles. Photo by Kevin Bennion, NREL. Anisotropic Thermal Measurement Study

  1. Oxidative Stress in Cardiac Mitochondria Caused by Copper Deficiency May Be Insufficient to Damage Mitochondrial Proteins

    USDA-ARS?s Scientific Manuscript database

    Copper (Cu) deficiency may promote the generation of reactive oxygen species (ROS) by the mitochondrial electron transport chain through inhibition of cytochrome c oxidase (CCO) and increased reduction of respiratory complexes upstream from CCO. In the present study, respiration, H2O2 production and...

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

    A central composite experimental design and response surface method were used to investigate the combined effects of water temperature (18-34°C) and copper ion concentration (0.1-1.5 mg/L) on the catalase (CAT) activity in the digestive gland of Crassostrea ariakensis. The results showed that the linear effects of temperature were significant ( P<0.01), the quadratic effects of temperature were significant ( P<0.05), the linear effects of copper ion concentration were not significant ( P>0.05), and the quadratic effects of copper ion concentration were significant ( P<0.05). Additionally, the synergistic effects of temperature and copper ion concentration were not significant ( P>0.05), and the effect of temperature was greater than that of copper ion concentration. A model equation of CAT enzyme activity in the digestive gland of C. ariakensis toward the two factors of interest was established, with R 2, Adj. R 2 and Pred. R 2 values as high as 0.943 7, 0.887 3 and 0.838 5, respectively. These findings suggested that the goodness of fit to experimental data and predictive capability of the model were satisfactory, and could be practically applied for prediction under the conditions of the study. Overall, the results suggest that the simultaneous variation of temperature and copper ion concentration alters the activity of the antioxidant enzyme CAT by modulating active oxygen species metabolism, which may be utilized as a biomarker to detect the effects of copper pollution.

  3. Comparative Investigation of Copper Tolerance and Identification of Putative Tolerance Related Genes in Tardigrades

    PubMed Central

    Hygum, Thomas L.; Fobian, Dannie; Kamilari, Maria; Jørgensen, Aslak; Schiøtt, Morten; Grosell, Martin; Møbjerg, Nadja

    2017-01-01

    Tardigrades are microscopic aquatic animals renowned for their tolerance toward extreme environmental conditions. The current study is the first to investigate their tolerance toward heavy metals and we present a novel tardigrade toxicant tolerance assay based on activity assessments as a measure of survival. Specifically, we compare tolerance toward copper in four species representing different evolutionary lineages, habitats and adaptation strategies, i.e., a marine heterotardigrade, Echiniscoides sigismundi, a limno-terrestrial heterotardigrade, Echiniscus testudo, a limno-terrestrial eutardigrade, Ramazzottius oberhaeuseri, and a marine eutardigrade, Halobiotus crispae. The latter was sampled at a time of year, when the population is predominantly represented by aberrant P1 cysts, while the other species were in normal active states prior to exposure. Based on volume measurements and a general relation between body mass and copper tolerance, expected tardigrade EC50 values were estimated at 0.5–2 μg l−1. Following 24 h of exposure, tolerance was high with no apparent link to lineage or habitat. EC50s (95% CI), 24 h after exposure, were estimated at 178 (168–186) and 310 (295–328) μg l−1, respectively, for E. sigismundi and R. oberhaeuseri, whereas E. testudo and H. crispae were less affected. Highest tolerance was observed in H. crispae with a mean ± s.e.m. activity of 77 ± 2% (n = 3) 24 h after removal from ~3 mg l−1 copper, suggesting that tardigrade cysts have increased tolerance toward toxicants. In order to identify putative tolerance related genes, an E. sigismundi transcriptome was searched for key enzymes involved in osmoregulation, antioxidant defense and copper metabolism. We found high expression of Na/K ATPase and carbonic anhydrase, known targets for copper. Our transcriptome, furthermore, revealed high expression of antioxidant enzymes, copper transporters, ATOX1, and a Cu-ATPase. In summary, our results indicate that tardigrades express well-known key osmoregulatory enzymes, supporting the hypothesis that copper inhibits sodium turnover as demonstrated for other aquatic organisms. Tardigrades, nevertheless, have high tolerance toward the toxicant, which is likely linked to high expression of antioxidant enzymes and an ability to enter dormant states. Tardigrades, furthermore, seem to have a well-developed battery of cuproproteins involved in copper homeostasis, providing basis for active copper sequestering and excretion. PMID:28293195

  4. Comparative Investigation of Copper Tolerance and Identification of Putative Tolerance Related Genes in Tardigrades.

    PubMed

    Hygum, Thomas L; Fobian, Dannie; Kamilari, Maria; Jørgensen, Aslak; Schiøtt, Morten; Grosell, Martin; Møbjerg, Nadja

    2017-01-01

    Tardigrades are microscopic aquatic animals renowned for their tolerance toward extreme environmental conditions. The current study is the first to investigate their tolerance toward heavy metals and we present a novel tardigrade toxicant tolerance assay based on activity assessments as a measure of survival. Specifically, we compare tolerance toward copper in four species representing different evolutionary lineages, habitats and adaptation strategies, i.e., a marine heterotardigrade, Echiniscoides sigismundi , a limno-terrestrial heterotardigrade, Echiniscus testudo , a limno-terrestrial eutardigrade, Ramazzottius oberhaeuseri , and a marine eutardigrade, Halobiotus crispae . The latter was sampled at a time of year, when the population is predominantly represented by aberrant P1 cysts, while the other species were in normal active states prior to exposure. Based on volume measurements and a general relation between body mass and copper tolerance, expected tardigrade EC50 values were estimated at 0.5-2 μg l -1 . Following 24 h of exposure, tolerance was high with no apparent link to lineage or habitat. EC50s (95% CI), 24 h after exposure, were estimated at 178 (168-186) and 310 (295-328) μg l -1 , respectively, for E. sigismundi and R. oberhaeuseri , whereas E. testudo and H. crispae were less affected. Highest tolerance was observed in H. crispae with a mean ± s.e.m . activity of 77 ± 2% ( n = 3) 24 h after removal from ~3 mg l -1 copper, suggesting that tardigrade cysts have increased tolerance toward toxicants. In order to identify putative tolerance related genes, an E. sigismundi transcriptome was searched for key enzymes involved in osmoregulation, antioxidant defense and copper metabolism. We found high expression of Na/K ATPase and carbonic anhydrase, known targets for copper. Our transcriptome, furthermore, revealed high expression of antioxidant enzymes, copper transporters, ATOX1, and a Cu-ATPase. In summary, our results indicate that tardigrades express well-known key osmoregulatory enzymes, supporting the hypothesis that copper inhibits sodium turnover as demonstrated for other aquatic organisms. Tardigrades, nevertheless, have high tolerance toward the toxicant, which is likely linked to high expression of antioxidant enzymes and an ability to enter dormant states. Tardigrades, furthermore, seem to have a well-developed battery of cuproproteins involved in copper homeostasis, providing basis for active copper sequestering and excretion.

  5. Newer systems for bacterial resistances to toxic heavy metals.

    PubMed Central

    Silver, S; Ji, G

    1994-01-01

    Bacterial plasmids contain specific genes for resistances to toxic heavy metal ions including Ag+, AsO2-, AsO4(3-), Cd2+, Co2+, CrO4(2-), Cu2+, Hg2+, Ni2+, Pb2+, Sb3+, and Zn2+. Recent progress with plasmid copper-resistance systems in Escherichia coli and Pseudomonas syringae show a system of four gene products, an inner membrane protein (PcoD), an outer membrane protein (PcoB), and two periplasmic Cu(2+)-binding proteins (PcoA and PcoC). Synthesis of this system is governed by two regulatory proteins (the membrane sensor PcoS and the soluble responder PcoR, probably a DNA-binding protein), homologous to other bacterial two-component regulatory systems. Chromosomally encoded Cu2+ P-type ATPases have recently been recognized in Enterococcus hirae and these are closely homologous to the bacterial cadmium efflux ATPase and the human copper-deficiency disease Menkes gene product. The Cd(2+)-efflux ATPase of gram-positive bacteria is a large P-type ATPase, homologous to the muscle Ca2+ ATPase and the Na+/K+ ATPases of animals. The arsenic-resistance system of gram-negative bacteria functions as an oxyanion efflux ATPase for arsenite and presumably antimonite. However, the structure of the arsenic ATPase is fundamentally different from that of P-type ATPases. The absence of the arsA gene (for the ATPase subunit) in gram-positive bacteria raises questions of energy-coupling for arsenite efflux. The ArsC protein product of the arsenic-resistance operons of both gram-positive and gram-negative bacteria is an intracellular enzyme that reduces arsenate [As(V)] to arsenite [As(III)], the substrate for the transport pump. Newly studied cation efflux systems for Cd2+, Zn2+, and Co2+ (Czc) or Co2+ and Ni2+ resistance (Cnr) lack ATPase motifs in their predicted polypeptide sequences. Therefore, not all plasmid-resistance systems that function through toxic ion efflux are ATPases. The first well-defined bacterial metallothionein was found in the cyanobacterium Synechococcus. Bacterial metallothionein is encoded by the smtA gene and contains 56 amino acids, including nine cysteine residues (fewer than animal metallothioneins). The synthesis of Synechococcus metallothionein is regulated by a repressor protein, the product of the adjacent but separately transcribed smtB gene. Regulation of metallothionein synthesis occurs at different levels; quickly by derepression of repressor activity, or over a longer time by deletion of the repressor gene at fixed positions and by amplification of the metallothionein DNA region leading to multiple copies of the gene. PMID:7843081

  6. Biphasic modulation of atherosclerosis induced by graded dietary copper supplementation in the cholesterol-fed rabbit

    PubMed Central

    LAMB, DAVID J; AVADES, TONY Y; FERNS, GORDON AA

    2001-01-01

    There has been considerable debate about how copper status may affect the biochemical and cellular processes associated with atherogenesis. We have investigated the effects of graded dietary copper supplementation on processes likely to contribute to atherogenesis, using the cholesterol-fed New Zealand White rabbit model. Rabbits (n = 40) were fed a 0.25–1% cholesterol diet deficient in copper. Animals received either 0, 1, 3 or 20 mg copper/day and were killed after 13 weeks. Plasma cholesterol levels were similar in each dietary group. Aortic concentrations of copper were higher in the 20 mg copper/day animals compared to those receiving 0 mg copper/day (3.70 ± 0.78 vs. 1.33 ± 0.46 µg/g wet tissue; P < 0.05). Aortic superoxide dismutase activity was higher in animals receiving 20 mg copper/day (323 ± 21 IU/mg tissue) compared to the other groups (187 ± 21; 239 ± 53; 201 ± 33 IU/mg tissue) (P > 0.05). En face staining of aortae with oil red O showed that both high copper supplementation (20 mg/day) (67.1 ± 5.5%) and a deficient diet (0 mg/day) (63.1 ± 4.8%) was associated with significantly larger lesions (P < 0.05) compared to moderately supplemented animals (1 mg/day and 3 mg/day) (51.3 ± 6.3 and 42.8 ± 7.9%). These data indicate that in the cholesterol-fed rabbit, there is an optimal dietary copper intake and that dietary copper deficiency or excess are associated with an increased susceptibility to aortic atherosclerosis. Many Western diets contain insufficient copper and these findings indicate that a moderate dietary copper content may confer a degree of cardiac protection to the human population. PMID:11703538

  7. Cuprous oxide nanoparticles trigger ER stress-induced apoptosis by regulating copper trafficking and overcoming resistance to sunitinib therapy in renal cancer.

    PubMed

    Yang, Qiwei; Wang, Ye; Yang, Qing; Gao, Yi; Duan, Xiaopeng; Fu, Qingcheng; Chu, Chuanmin; Pan, Xiuwu; Cui, Xingang; Sun, Yinghao

    2017-11-01

    While the current standard first-line treatment for advanced renal cell carcinoma (RCC) is sunitinib, patients inevitably develop resistance to this drug. However, the rapid development of nanotechnology has provided emerging techniques for the treatment of advanced tumours, including RCC. In our previous research, cuprous oxide nanoparticles (CONPs) showed ideal anti-tumour effects and low systemic toxicity. While many inorganic nanomedicines, including CONPs, have similar pharmacological effects, their detailed mechanisms remain unknown. Copper chaperone proteins, which regulate the endocellular dosage and transport of copper, also play crucial roles in the progression of cancer. In this research, we discovered that CONPs can disrupt copper transportation by regulating the copper chaperone proteins ATOX1 and CCS in RCC cells and induce endoplasmic reticulum (ER) stress in vitro and in vivo by promoting the accumulation of intracellular calcium and reactive oxygen species (ROS). Furthermore, CONPs can initiate ER- and mitochondrial-dependent apoptosis by activating caspase-3, caspase-9 and caspase-12. In addition, CONPs downregulate the expression of AXL, MET, AKT, and ERK to recover sunitinib responsiveness in RCC cells with sunitinib resistance (SR) and may therefore facilitate the development of promising new pathways to treat patients with acquired SRRCC. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Thin film solar cell configuration and fabrication method

    DOEpatents

    Menezes, Shalini

    2009-07-14

    A new photovoltaic device configuration based on an n-copper indium selenide absorber and a p-type window is disclosed. A fabrication method to produce this device on flexible or rigid substrates is described that reduces the number of cell components, avoids hazardous materials, simplifies the process steps and hence the costs for high volume solar cell manufacturing.

  9. Association of trace elements with lipid profiles and glycaemic control in patients with type 1 diabetes mellitus in northern Sardinia, Italy: An observational study.

    PubMed

    Peruzzu, Angela; Solinas, Giuliana; Asara, Yolande; Forte, Giovanni; Bocca, Beatrice; Tolu, Francesco; Malaguarnera, Lucia; Montella, Andrea; Madeddu, Roberto

    2015-08-01

    Sardinia is an Italian region with a high incidence of type 1 diabetes mellitus. This study aimed to determine the associations of trace elements with lipid profiles and glycaemic control in patients with T1DM. A total of 192 patients with T1DM who attended the Unit of Diabetology and Metabolic Diseases in Sassari, Italy, were enrolled. Trace elements zinc, copper, selenium, chromium, and iron were measured in whole blood by sector field inductively coupled plasma mass spectrometry. The correlations between metabolic variables and the levels of trace elements were determined. Zinc was positively correlated with total cholesterol (P=0.023), low-density lipoprotein (P=0.0015), and triglycerides (P=0.027). Iron as significantly correlated with TC (P=0.0189), LDL (P=0.0121), and high-density lipoprotein (HDL) (P=0.0466). In males, Cr was positively correlated with HDL (P=0.0079) and Se, in females was correlated with TG (P=0.0113). The mean fasting plasma glucose was166.2mgdL(-1). Chromium was correlated with fasting plasma glucose (P=0.0149), particularly in males (P=0.0038). Overall, 63.5% of the patients had moderate HbA1c (7-9%). Copper was significantly correlated with HbA1c% in males (P=0.0155). In conclusion, the results of this study indicate that trace elements show different associations with lipid levels and glycaemic control in T1DM. Zinc, Fe, and Se were associated with lipid levels whereas Cu and Cr were associated with HbA1c%. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Copper-Zinc-Tin-Sulfur Thin Film Using Spin-Coating Technology

    PubMed Central

    Yeh, Min-Yen; Lei, Po-Hsun; Lin, Shao-Hsein; Yang, Chyi-Da

    2016-01-01

    Cu2ZnSnS4 (CZTS) thin films were deposited on glass substrates by using spin-coating and an annealing process, which can improve the crystallinity and morphology of the thin films. The grain size, optical gap, and atomic contents of copper (Cu), zinc (Zn), tin (Sn), and sulfur (S) in a CZTS thin film absorber relate to the concentrations of aqueous precursor solutions containing copper chloride (CuCl2), zinc chloride (ZnCl2), tin chloride (SnCl2), and thiourea (SC(NH2)2), whereas the electrical properties of CZTS thin films depend on the annealing temperature and the atomic content ratios of Cu/(Zn + Sn) and Zn/Sn. All of the CZTS films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDXS), Raman spectroscopy, and Hall measurements. Furthermore, CZTS thin film was deposited on an n-type silicon substrate by using spin-coating to form an Mo/p-CZTS/n-Si/Al heterostructured solar cell. The p-CZTS/n-Si heterostructured solar cell showed a conversion efficiency of 1.13% with Voc = 520 mV, Jsc = 3.28 mA/cm2, and fill-factor (FF) = 66%. PMID:28773647

  11. The Intestinal Copper Exporter CUA-1 Is Required for Systemic Copper Homeostasis in Caenorhabditis elegans.

    PubMed

    Chun, Haarin; Sharma, Anuj Kumar; Lee, Jaekwon; Chan, Jefferson; Jia, Shang; Kim, Byung-Eun

    2017-01-06

    Copper plays key catalytic and regulatory roles in biochemical processes essential for normal growth, development, and health. Defects in copper metabolism cause Menkes and Wilson's disease, myeloneuropathy, and cardiovascular disease and are associated with other pathophysiological states. Consequently, it is critical to understand the mechanisms by which organisms control the acquisition, distribution, and utilization of copper. The intestinal enterocyte is a key regulatory point for copper absorption into the body; however, the mechanisms by which intestinal cells transport copper to maintain organismal copper homeostasis are poorly understood. Here, we identify a mechanism by which organismal copper homeostasis is maintained by intestinal copper exporter trafficking that is coordinated with extraintestinal copper levels in Caenorhabditis elegans Specifically, we show that CUA-1, the C. elegans homolog of ATP7A/B, localizes to lysosome-like organelles (gut granules) in the intestine under copper overload conditions for copper detoxification, whereas copper deficiency results in a redistribution of CUA-1 to basolateral membranes for copper efflux to peripheral tissues. Worms defective in gut granule biogenesis exhibit defects in copper sequestration and increased susceptibility to toxic copper levels. Interestingly, however, a splice isoform CUA-1.2 that lacks a portion of the N-terminal domain is targeted constitutively to the basolateral membrane irrespective of dietary copper concentration. Our studies establish that CUA-1 is a key intestinal copper exporter and that its trafficking is regulated to maintain systemic copper homeostasis. C. elegans could therefore be exploited as a whole-animal model system to study regulation of intra- and intercellular copper trafficking pathways. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  12. Hybrid Quantum Cascade Lasers on Silicon-on-Sapphire

    DTIC Science & Technology

    2016-11-23

    on-SOS devices mounted on a copper heat sink. The liquid crystal thermal absorber is attached to block mid-IR emission from any sections of the laser...directions. 2. Statement of the problem studied Short-wavelength infrared (SWIR, ~1-3 m) photonics systems based on silicon-on- insulator (SOI...Table 1. Layer type Layer thickness and doping Thickness (nm) Doping (cm-3) InP substrate 350000 Semi- insulating InP buffer layer 2000 2.00E

  13. Solution-grown organic single-crystalline p-n junctions with ambipolar charge transport.

    PubMed

    Fan, Congcheng; Zoombelt, Arjan P; Jiang, Hao; Fu, Weifei; Wu, Jiake; Yuan, Wentao; Wang, Yong; Li, Hanying; Chen, Hongzheng; Bao, Zhenan

    2013-10-25

    Organic single-crystalline p-n junctions are grown from mixed solutions. First, C60 crystals (n-type) form and, subsequently, C8-BTBT crystals (p-type) nucleate heterogeneously on the C60 crystals. Both crystals continue to grow simultaneously into single-crystalline p-n junctions that exhibit ambipolar charge transport characteristics. This work provides a platform to study organic single-crystalline p-n junctions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Bioavailability of trace elements in beans and zinc-biofortified wheat in pigs.

    PubMed

    Carlson, Dorthe; Nørgaard, Jan Værum; Torun, Bulent; Cakmak, Ismail; Poulsen, Hanne Damgaard

    2012-12-01

    The objectives of this experiment were to study bioavailability of trace elements in beans and wheat containing different levels of zinc and to study how the water solubility of trace elements was related to the bioavailability in pigs. Three wheat and two bean types were used: wheat of Danish origin as a control (CtrlW), two Turkish wheat types low (LZnW) and high (HZnW) in zinc, a common bean (Com), and a faba bean (Faba). Two diets were composed by combining 81 % CtrlW and 19 % Com or Faba beans. Solubility was measured as the trace element concentration in the supernatant of feedstuffs, and diets incubated in distilled water at pH 4 and 38°C for 3 h. The bioavailability of zinc and copper of the three wheat types and the two bean-containing diets were evaluated in the pigs by collection of urine and feces for 7 days. The solubility of zinc was 34-63 %, copper 18-42 %, and iron 3-11 %. The zinc apparent digestibility in pigs was similar in the three wheat groups (11-14 %), but was significantly higher in the CtrlW+Faba group (23 %) and negative in the CtrlW+Com group (-30 %). The apparent digestibility of copper was higher in the HZnW (27 %) and CtrlW+Faba (33 %) groups than in the CtrlW (17 %) and LZnW (18 %) groups. The apparent copper digestibility of the CtrlW+Com diet was negative (-7 %). The solubility and digestibility results did not reflect the concentration in feedstuffs. The in vitro results of water solubility showed no relationship to the results of trace mineral bioavailability in pigs.

  15. One-pot synthesis of active copper-containing carbon dots with laccase-like activities.

    PubMed

    Ren, Xiangling; Liu, Jing; Ren, Jun; Tang, Fangqiong; Meng, Xianwei

    2015-12-14

    Herein, an effective strategy for designing a new type of nanozyme, blue fluorescent laccase mimics, is reported. Active copper-containing carbon dots (Cu-CDs) were synthesized through a simple, nontoxic and one-pot hydrothermal method, which showed favorable photoluminescence properties and good photostability under high-salt conditions or in a broad pH range (3.0-13.5). The Cu-CDs possessed intrinsic laccase-like activities and could catalyze the oxidation of the laccase substrate p-phenylenediamine (PPD) to produce a typical color change from colorless to brown. Poly(methacrylic acid sodium salt) (PMAA) not only was used as the carbon source and reducing agent, but also provided carboxyl groups to assist flocculation between Cu-CDs and polyacrylamide, which facilitated the removal of PPD. Importantly, the intrinsic fluorescence of the as-prepared Cu-CDs could indicate the presence of hydroquinone, one of the substrates of laccases, based on laccase mimics and fluorescence quenching.

  16. 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.

  17. 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

  18. 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.

  19. Free Energy Defect Model for the Cu-In-Ga-Se Tetrahedral Lattice

    NASA Astrophysics Data System (ADS)

    Stanbery, B. J.

    2003-03-01

    The most efficient thin-film photovoltaic converters of solar insolation to electrical power have recently achieved conversion efficiencies exceeding 19%, and are based on light absorbing layers containing the binary alloy (CuInSe_2)_1-X(CuGaSe_2)X of the α phases of these ternary chalcopyrite compounds. A statistical quantum mechanical model of the thermodynamic equilibrium defect structure of the tetrahedral lattice of copper, indium, and selenium with composition in the domain between that of the stoichiometric CuIn_1-XGa_XSe2 alloy and the β phase Cu(In_1-XGa_X)_3Se5 composition is presented. Compositions more copper-deficient than the latter have been reported experimentally to result in a breakdown of the tetrahedral coordination characteristic of the chalcopyrite lattice. These computations are based on a cluster expansion algorithm that minimizes the total free energy of the system using the Gibbs-Duhem equation to compute quasichemical reaction equilibria between the neutral clusters, and explicitly incorporates Fermi-Dirac statistics to determine their ionization equilibria and consequent carrier concentrations in the conduction and valence bands. The results are consistent with recent experimental evidence that the stoichiometric CuIn_1-XGa_XSe2 composition segregates in equilibrium into a two-phase mixture of a copper-deficient quaternary Cu_1-γIn_1-XGa_XSe2 composition and the binary Cu_2-δSe compound. The model predicts that the hole majority carrier (p-type) can only be achieved in the equilibrium single-phase chalcopyrite lattice with compositions that correspond to Cu_1-γIn_1-XGa_XSe_2+ɛ with γ and ɛ >0. This predicted requirement for selenium enrichment compared to the stoichiometric CuIn_1-XGa_XSe2 alloy composition for the dominance of holes over electrons as the majority carrier type is consistent with experimental evidence, and is explained in terms of a transition of the dominant lattice defect from the selenium vacancy in the stoichiometric case to the copper vacancy defect in the selenium-enriched lattice. This result is of particular importance since all CuIn_1-XGa_XSe2 thin-film solar cells utilize p-type absorber films.

  20. Catalytic and inhibiting effect of amino acids on the porphyrin metallation reactions

    NASA Astrophysics Data System (ADS)

    Mamardashvili, Galina M.; Zhdanova, Daria Yu.; Mamardashvili, Nugzar Zh.; Koifman, Oskar I.; Dehaen, Wim

    In the present work, using the interaction of tetra-(4-sulfophenyl)porphyrin with copper(II) chloride as an example, it has been shown how different amino acid additives (glycine, valine, leucine and tryptophan) catalyze or inhibit the formation of Cu-porphyrin as a function of the chemical environment (borate buffer (pH7.4), DMSO) and the concentration of the additive. It has been demonstrated that the type of amino acid affects the complexation reaction rate. Possible mechanisms of metalloporphyrin formation and the ways of their acceleration are discussed. Ways in which different amino acid additives catalyze or inhibit the interaction of tetra-(4-sulfophenyl)porphyrin with copper(II) chloride are examined.

  1. Gold and copper partitioning in magmatic-hydrothermal systems at 800 °C and 100 MPa

    NASA Astrophysics Data System (ADS)

    Frank, Mark R.; Simon, Adam C.; Pettke, Thomas; Candela, Philip A.; Piccoli, Philip M.

    2011-05-01

    Porphyry-type ore deposits sometimes contain fluid inclusion compositions consistent with the partitioning of copper and gold into vapor relative to coexisting brine at the depositional stage. However, this has not been reproduced experimentally at magmatic conditions. In an attempt to determine the conditions under which copper and gold may partition preferentially into vapor relative to brine at temperatures above the solidus of granitic magmas, we performed experiments at 800 °C, 100 MPa, oxygen fugacity ( fO2sys) buffered by Ni-NiO, and aS2sys fixed at either 3.5 × 10 -2 by using intermediate solid solution-pyrrhotite, or 1.2 × 10 -4 by using intermediate solid solution-pyrrhotite-bornite. The coexisting vapor (˜3 wt.% NaCl eq.) and brine (˜68 wt.% NaCl eq.) were composed initially of NaCl + KCl + HCl + H 2O, with starting HCl set to <1000 μg/g in the aqueous mixture. Synthetic vapor and brine fluid inclusions were trapped at run conditions and subsequently analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Our experiments demonstrate that copper and gold partitioned strongly into the magmatic volatile phase(s) (MVP) (i.e., vapor or brine) relative to a silicate melt over the entire imposed range of aS2sys. Nernst style partition coefficients between coexisting brine (b) and melt (m), D b/m (±1 σ), range from 3.6(±2.2) × 10 1 to 4(±2) × 10 2 for copper and from 1.2(±0.6) × 10 2 to 2.4(±2.4) × 10 3 for gold. Partition coefficients between coexisting vapor (v) and melt, D v/m range from 2.1 ± 0.7 to 18 ± 5 and 7(±3) × 10 1 to 1.6(±1.6) × 10 2 for copper and gold, respectively. Partition coefficients for all experiments between coexisting brine and vapor, D b/v (±1 σ), range from 7(±2) to 1.0(±0.4) × 10 2 and 1.7(±0.2) to 15(±2) for copper and gold, respectively. Observed average D b/v at an aS2sys of 1.2 × 10 -4 were elevated, 95(±5) and 15 ± 1 for copper and gold, respectively, relative to those at the higher aS2sys of 3.5 × 10 -2 where D b/v were 10(±5) for copper and 7(±6) for gold. Thus, there is an inverse relationship between the aS2sys and the D b/v for both copper and gold with increasing aS2sys resulting in a decrease in the D b/v signifying increased importance of the vapor phase for copper and gold transport. This suggests that copper and gold may complex with volatile S-species as well as Cl-species at magmatic conditions, however, none of the experiments of our study at 800 °C and 100 MPa had a D b/v ⩽ 1. We did not directly determine speciation, but infer the existence of some metal-sulfur complexes based on the reported data. We suggest that copper and gold partition preferentially into the brine in most instances at or above the wet solidus. However, in most systems, the mass of vapor is greater than the mass of brine, and vapor transport of copper and gold may become more important in the magmatic environment at higher aS2sys, lower fO2sys, or near the critical point in a salt-water system. A D b/v ⩽ 1 at subsolidus hydrothermal conditions may also occur in response to changes in temperature, fO2sys, aS2sys, and/or acidity. Additionally, both copper and gold were observed to partition into intermediate solid solution and bornite much more strongly than into vapor, brine or silicate melt. This suggests that, although vapor and brine are both efficient at removing copper and gold from a silicate melt, the presence of Cu-Fe sulfides can sequester a substantial portion of the copper and gold contained within a silicate melt if the Cu-Fe sulfides are abundant.

  2. 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

  3. [Mechanism of oxidation reaction of NADH models and phynylglyoxal with hydrogen peroxide. Hypothesis on separate transport of hydrogen and electron atom in certain enzymatic reactions with the participation of NADH and NADPH].

    PubMed

    Iasnikov, A A; Ponomarenko, S P

    1976-05-01

    Kinetics of co-oxidation of 1-benzen-3-carbamido-1,4-dihydropyridine (BDN) and phenylglyoxal (PG) with hydrogen peroxide is studied. Dimeric product (di-e11-benzen-5-carbamido-1,2-dihydropyridyl-2]) is found to be formed at pH 9, and quaternal pyridinium salt (BNA)--at pH 7. Molecular oxigen is determined to participate in the reaction at pH 7. Copper (II) ions catalyze this process. Significant catalytic effect of p-dinitrobenzen (p-DNB) is found. The reaction mechanism is postulated to form hydroperoxide from PG and hydrogen peroxide which are capable to split the hydrogen attom from dihydropyridine, molecular oxigen or p-DNB being an acceptor of the electrone. Hypothesis on separate transfer of hydrogen atom and electrone in biological systems are proposed.

  4. Copper stabilization in beneficial use of waterworks sludge and copper-laden electroplating sludge for ceramic materials.

    PubMed

    Tang, Yuanyuan; Chan, Siu-Wai; Shih, Kaimin

    2014-06-01

    A promising strategy for effectively incorporating metal-containing waste materials into a variety of ceramic products was devised in this study. Elemental analysis confirmed that copper was the predominant metal component in the collected electroplating sludge, and aluminum was the predominant constituent of waterworks sludge collected in Hong Kong. The use of waterworks sludge as an aluminum-rich precursor material to facilitate copper stabilization under thermal conditions provides a promising waste-to-resource strategy. When sintering the mixture of copper sludge and the 900 °C calcined waterworks sludge, the CuAl2O4 spinel phase was first detected at 650 °C and became the predominant product phase at temperatures higher than 850 °C. Quantification of the XRD pattern using the Rietveld refinement method revealed that the weight of the CuAl2O4 spinel phase reached over 50% at 850 °C. The strong signals of the CuAl2O4 phase continued until the temperature reached 1150 °C, and further sintering initiated the generation of the other copper-hosting phases (CuAlO2, Cu2O, and CuO). The copper stabilization effect was evaluated by the copper leachability of the CuAl2O4 and CuO via the prolonged leaching experiments at a pH value of 4.9. The leaching results showed that the CuAl2O4 phase was superior to the CuAlO2 and CuO phases for immobilizing hazardous copper over longer leaching periods. The findings clearly indicate that spinel formation is the most crucial metal stabilization mechanism when sintering multiphase copper sludge with aluminum-rich waterworks sludge, and suggest a promising and reliable technique for reusing both types of sludge waste for ceramic materials. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Effect of arbuscular mycorrhizal fungi on young vines in copper-contaminated soil

    PubMed Central

    Ambrosini, Vítor Gabriel; Voges, Joana Gerent; Canton, Ludiana; Couto, Rafael da Rosa; Ferreira, Paulo Ademar Avelar; Comin, Jucinei José; de Melo, George Wellington Bastos; Brunetto, Gustavo; Soares, Cláudio Roberto Fonsêca Sousa

    2015-01-01

    Abstract High copper (Cu) levels in uprooted old vineyard soils may cause toxicity in transplanted young vines, although such toxicity may be reduced by inoculating plants with arbuscular mycorrhizal fungi (AMF). The objective of this study was to evaluate the effects of AMF on the plant growth, chlorophyll contents, mycorrhizal colonization, and Cu and phosphorus (P) absorption in young vines cultivated in a vineyard soil contaminated by Cu. Commercial vineyard soil with high Cu levels was placed in plastic tubes and transplanted with young vines, which were inoculated with six AMF species (Dentiscutata heterogama, Gigaspora gigantea, Acaulospora morrowiae, A. colombiana, Rhizophagus clarus, R. irregularis) and a control treatment on randomized blocks with 12 replicates. After 130 days, the mycorrhizal colonization, root and shoot dry matter (DM), height increment, P and Cu absorption, and chlorophyll contents were evaluated. The height increment, shoot DM and chlorophyll contents were not promoted by AMF, although the root DM was increased by R. clarus and R. irregularis, which had the greatest mycorrhizal colonization and P uptake. AMF increased Cu absorption but decreased its transport to shoots. Thus, AMF species, particularly R. clarus and R. irregularis, contribute to the establishment of young vines exposed to high Cu levels. PMID:26691462

  6. Effects of copper vapour on thermophysical properties of CO2-N2 plasma

    NASA Astrophysics Data System (ADS)

    Zhong, Linlin; Wang, Xiaohua; Rong, Mingzhe; Cressault, Yann

    2016-10-01

    CO2-N2 mixtures are often used as arc quenching medium (to replace SF6) in circuit breakers and shielding gas in arc welding. In such applications, copper vapour resulting from electrode surfaces can modify characteristics of plasmas. This paper therefore presents an investigation of the effects of copper on thermophysical properties of CO2-N2 plasma. The equilibrium compositions, thermodynamic properties (including mass density, specific enthalpy, and specific heat), transport coefficients (including electrical conductivity, viscosity, and thermal conductivity), and four kinds of combined diffusion coefficients due to composition gradients, applied electric fields, temperature gradients, and pressure gradients respectively, were calculated and discussed for CO2-N2 (mixing ratio 7:3) plasma contaminated by different proportions of copper vapour. The significant influences of copper were observed on all the properties of CO2-N2-Cu mixtures. The better ionization ability and larger molar mass of copper and larger collision integrals related to copper, should be responsible for such influences.

  7. Glutamic acid leaching of synthetic covellite - A model system combining experimental data and geochemical modeling.

    PubMed

    Barthen, R; Karimzadeh, L; Gründig, M; Grenzer, J; Lippold, H; Franke, K; Lippmann-Pipke, J

    2018-04-01

    For Kupferschiefer mining established pyrometallurgical and acidic bioleaching methods face numerous problems. This is due to the finely grained and dispersed distribution of the copper minerals, the complex mineralogy, comparably low copper content, and the possibly high carbonate and organic content in this ore. Leaching at neutral pH seemed worth a try: At neutral pH the abundant carbonates do not need to be dissolved and therewith would not consume excessive amounts of provided acids. Certainly, copper solubility at neutral pH is reduced compared to an acidic environment; however, if copper complexing ligands would be supplied abundantly, copper contents in the mobile phase could easily reach the required economic level. We set up a model system to study the effect of parameters such as pH, microorganisms, microbial metabolites, and organic ligands on covellite leaching to get a better understanding of the processes in copper leaching at pH ≥ 6. With this model system we could show that glutamic acid and the microbial siderophore desferrioxamine B promote covellite dissolution. Both experimental and modeling data showed that pH is an important parameter in covellite dissolution. An increase of pH from 6 to 9 could elevate copper extraction in the presence of glutamic acid by a factor of five. These results have implications for both development of a biotechnological process regarding metal extraction from Kupferschiefer, and for the interaction of bacterial metabolites with the lithosphere and potential mobilization of heavy metals in alkaline environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. 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.

  9. 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.

  10. A multicopper oxidase contributes to the copper tolerance of Brucella melitensis 16M.

    PubMed

    Wu, Tonglei; Wang, Shaohua; Wang, Zhen; Peng, Xiaowei; Lu, Yanli; Wu, Qingmin

    2015-06-01

    Copper is a potent antimicrobial agent. Multiple mechanisms of copper tolerance are utilized by some pathogenic bacteria. BMEII0580, which is significantly similar to the multicopper oxidase from Escherichia coli, was predicted to be the probable blue copper protein YacK precursor in Brucella melitensis 16M, and was designated as Brucella multicopper oxidase (BmcO). A bioinformatics analysis indicated that the typical motifs of multicopper oxidases are present in BmcO. BmcO, the expression of which was up-regulated by copper, could catalyze the oxidation of 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), dimethoxyphenol (DMP) and para-phenylenediamine (pPD), which are widely used as substrates for multicopper oxidase. Additionally, BmcO exhibited ferroxidase activity, which indicated that it might play an important role in the Fe(2+) uptake of B. melitensis. Importantly, the mutant strain 16MΔbmcO was more sensitive to copper than the wild-type strain B. melitensis 16M as well as its complementation strain 16MΔbmcO(bmcO). The infection assays of cells showed that similar bacterial numbers of B. melitensis 16M, 16MΔbmcO and 16MΔbmcO(bmcO) strains were recovered from the infected macrophages. This result indicated that BmcO was not essential for B. melitensis intracellular growth. In conclusion, our results confirm that BmcO is a multicopper oxidase and contributes to the copper tolerance of B. melitensis 16M. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

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

    PubMed

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

    2014-07-07

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

  12. Application of cotton as a solid phase extraction sorbent for on-line preconcentration of copper in water samples prior to inductively coupled plasma optical emission spectrometry determination.

    PubMed

    Faraji, Mohammad; Yamini, Yadollah; Shariati, Shahab

    2009-07-30

    Copper, as a heavy metal, is toxic for many biological systems. Thus, the determination of trace amounts of copper in environmental samples is of great importance. In the present work, a new method was developed for the determination of trace amounts of copper in water samples. The method is based on the formation of ternary Cu(II)-CAS-CTAB ion-pair and adsorption of it into a mini-column packed with cotton prior applying inductively coupled plasma optical emission spectrometry (ICP-OES). The experimental parameters that affected the extraction efficiency of the method such as pH, flow rate and volume of the sample solution, concentration of chromazurol S (CAS) and cethyltrimethylammonium bromide (CTAB) as well as type and concentration of eluent were investigated and optimized. The ion-pair (Cu(II)-CAS-CTAB) was quantitatively retained on the cotton under the optimum conditions, then eluted completely using a solution of 25% (v/v) 1-propanol in 0.5 mol L(-1) HNO(3) and directly introduced into the nebulizer of the ICP-OES. The detection limit (DL) of the method for copper was 40 ng L(-1) (V(sample)=100mL) and the relative standard deviation (R.S.D.) for the determination of copper at 10 microg L(-1) level was found to be 1.3%. The method was successfully applied to determine the trace amounts of copper in tap water, deep well water, seawater and two different mineral waters, and suitable recoveries were obtained (92-106%).

  13. Sol-gel synthesis of Cu-doped p-CdS nanoparticles and their analysis as p-CdS/n-ZnO thin film photodiode

    NASA Astrophysics Data System (ADS)

    Arya, Sandeep; Sharma, Asha; Singh, Bikram; Riyas, Mohammad; Bandhoria, Pankaj; Aatif, Mohammad; Gupta, Vinay

    2018-05-01

    Copper (Cu) doped p-CdS nanoparticles have been synthesized via sol-gel method. The as-synthesized nanoparticles were successfully characterized and implemented for fabrication of Glass/ITO/n-ZnO/p-CdS/Al thin film photodiode. The fabricated device is tested for small (-1 V to +1 V) bias voltage. Results verified that the junction leakage current within the dark is very small. During reverse bias condition, the maximum amount of photocurrent is obtained under illumination of 100 μW/cm2. Electrical characterizations confirmed that the external quantum efficiency (EQE), gain and responsivity of n-ZnO/p-CdS photodiode show improved photo response than conventional p-type materials for such a small bias voltage. It is therefore revealed that the Cu-doped CdS nanoparticles is an efficient p-type material for fabrication of thin film photo-devices.

  14. Nanotechnologies for efficient solar and wind energy harvesting and storage

    NASA Astrophysics Data System (ADS)

    Eldada, Louay A.

    2010-08-01

    We describe nanotechnologies used to improve the efficient harvest of energy from the Sun and the wind, and the efficient storage of energy in secondary batteries and ultracapacitors, for use in a variety of applications including smart grids, electric vehicles, and portable electronics. We demonstrate high-quality nanostructured copper indium gallium selenide (CIGS) thin films for photovoltaic (PV) applications. The self-assembly of nanoscale p-n junction networks creates n-type networks that act as preferential electron pathways, and p-type networks that act as preferential hole pathways, allowing positive and negative charges to travel to the contacts in physically separated paths, reducing charge recombination. We also describe PV nanotechnologies used to enhance light trapping, photon absorption, charge generation, charge transport, and current collection. Furthermore, we describe nanotechnologies used to improve the efficiency of power-generating wind turbines. These technologies include nanoparticle-containing lubricants that reduce the friction generated from the rotation of the turbines, nanocoatings for de-icing and self-cleaning technologies, and advanced nanocomposites that provide lighter and stronger wind blades. Finally, we describe nanotechnologies used in advanced secondary batteries and ultracapacitors. Nanostructured powder-based and carbon-nanotube-based cathodes and anodes with ultra-high surface areas boost the energy and power densities in secondary batteries, including lithium-ion and sodium-sulfur batteries. Nanostructured carbon materials are also controlled on a molecular level to offer large surface areas for the electrodes of ultracapacitors, allowing to store and supply large bursts of energy needed in some applications.

  15. Molecular and biochemical characterization of a unique mutation in CCS, the human copper chaperone to superoxide dismutase.

    PubMed

    Huppke, Peter; Brendel, Cornelia; Korenke, Georg Christoph; Marquardt, Iris; Donsante, Anthony; Yi, Ling; Hicks, Julia D; Steinbach, Peter J; Wilson, Callum; Elpeleg, Orly; Møller, Lisbeth Birk; Christodoulou, John; Kaler, Stephen G; Gärtner, Jutta

    2012-08-01

    Copper (Cu) is a trace metal that readily gains and donates electrons, a property that renders it desirable as an enzyme cofactor but dangerous as a source of free radicals. To regulate cellular Cu metabolism, an elaborate system of chaperones and transporters has evolved, although no human Cu chaperone mutations have been described to date. We describe a child from a consanguineous family who inherited homozygous mutations in the SLC33A1, encoding an acetyl CoA transporter, and in CCS, encoding the Cu chaperone for superoxide dismutase. The CCS mutation, p.Arg163Trp, predicts substitution of a highly conserved arginine residue at position 163, with tryptophan in domain II of CCS, which interacts directly with superoxide dismutase 1 (SOD1). Biochemical analyses of the patient's fibroblasts, mammalian cell transfections, immunoprecipitation assays, and Lys7Δ (CCS homolog) yeast complementation support the pathogenicity of the mutation. Expression of CCS was reduced and binding of CCS to SOD1 impaired. As a result, this mutation causes reduced SOD1 activity and may impair other mechanisms important for normal Cu homeostasis. CCS-Arg163Trp represents the primary example of a human mutation in a gene coding for a Cu chaperone. © 2012 Wiley Periodicals, Inc.

  16. Physiological and molecular responses to heavy metal stresses suggest different detoxification mechanism of Populus deltoides and P. x canadensis.

    PubMed

    Benyó, Dániel; Horváth, Edit; Németh, Edit; Leviczky, Tünde; Takács, Kinga; Lehotai, Nóra; Feigl, Gábor; Kolbert, Zsuzsanna; Ördög, Attila; Gallé, Róbert; Csiszár, Jolán; Szabados, László; Erdei, László; Gallé, Ágnes

    2016-08-20

    Plants have divergent defense mechanisms against the harmful effects of heavy metals present in excess in soils and groundwaters. Poplars (Populus spp.) are widely cultivated because of their rapid growth and high biomass production, and members of the genus are increasingly used as experimental model organisms of trees and for phytoremediation purposes. Our aim was to investigate the copper and zinc stress responses of three outstanding biomass producer bred poplar lines to identify such transcripts of genes involved in the detoxification mechanisms, which can play an important role in the protection against heavy metals. Poplar cuttings were grown hydroponically and subjected to short-term (one week) mild and sublethal copper and zinc stresses. We evaluated the effects of the applied heavy metals and the responses of plants by detecting the changes of multiple physiological and biochemical parameters. The most severe cellular oxidative damage was caused by 30μM copper treatment, while zinc was less harmful. Analysis of stress-related transcripts revealed genotype-specific differences that are likely related to alterations in heavy metal tolerance. P. deltoides clones B-229 and PE 19/66 clones were clearly more effective at inducing the expression of various genes implicated in the detoxification process, such as the glutathione transferases, metallothioneins, ABC transporters, (namely PtGSTU51, PxMT1, PdABCC2,3), while the P. canadensis line M-1 accumulated more metal, resulting in greater cellular oxidative damage. Our results show that all three poplar clones are efficient in stress acclimatization, but with different molecular bases. Copyright © 2016 Elsevier GmbH. All rights reserved.

  17. 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.

  18. 76 FR 18542 - Copper Valley Electric Association; Notice of Scoping Document 2 and Soliciting Scoping Comments...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-04

    ... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Project No. 13124-002] Copper Valley.... Applicant: Copper Valley Electric Association (Copper Valley) d. Name of Project: Allison Creek Project. e.... 791(a)-825(r). g. Applicant Contact: Robert A. Wilkinson, CEO, Copper Valley Electric Association, P.O...

  19. Multi-group Fokker-Planck proton transport in MCNP{trademark}

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

    Adams, K.J.

    1997-11-01

    MCNP has been enhanced to perform proton transport using a multigroup Fokker Planck (MGFP) algorithm with primary emphasis on proton radiography simulations. The new method solves the Fokker Planck approximation to the Boltzmann transport equation for the small angle multiple scattering portion of proton transport. Energy loss is accounted for by applying a group averaged stopping power over each transport step. Large angle scatter and non-inelastic events are treated as extinction. Comparisons with the more rigorous LAHET code show agreement to a few per cent for the total transmitted currents. The angular distributions through copper and low Z compounds showmore » good agreement between LAHET and MGFP with the MGFP method being slightly less forward peaked and without the large angle tails apparent in the LAHET simulation. Suitability of this method for proton radiography simulations is shown for a simple problem of a hole in a copper slab. LAHET and MGFP calculations of position, angle and energy through more complex objects are presented.« less

  20. Thermophysical analysis for three-dimensional MHD stagnation-point flow of nano-material influenced by an exponential stretching surface

    NASA Astrophysics Data System (ADS)

    Ur Rehman, Fiaz; Nadeem, Sohail; Ur Rehman, Hafeez; Ul Haq, Rizwan

    2018-03-01

    In the present paper a theoretical investigation is performed to analyze heat and mass transport enhancement of water-based nanofluid for three dimensional (3D) MHD stagnation-point flow caused by an exponentially stretched surface. Water is considered as a base fluid. There are three (3) types of nanoparticles considered in this study namely, CuO (Copper oxide), Fe3O4 (Magnetite), and Al2O3 (Alumina) are considered along with water. In this problem we invoked the boundary layer phenomena and suitable similarity transformation, as a result our three dimensional non-linear equations of describing current problem are transmuted into nonlinear and non-homogeneous differential equations involving ordinary derivatives. We solved the final equations by applying homotopy analysis technique. Influential outcomes of aggressing parameters involved in this study, effecting profiles of temperature field and velocity are explained in detail. Graphical results of involved parameters appearing in considered nanofluid are presented separately. It is worth mentioning that Skin-friction along x and y-direction is maximum for Copper oxide-water nanofluid and minimum for Alumina-water nanofluid. Result for local Nusselt number is maximum for Copper oxide-water nanofluid and is minimum for magnetite-water nanofluid.

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