H2 gas sensing properties of a ZnO/CuO and ZnO/CuO/Cu2O Heterostructures

NASA Astrophysics Data System (ADS)

Ababii, N.; Postica, V.; Hoppe, M.; Adelung, R.; Lupan, O.; Railean, S.; Pauporté, T.; Viana, B.

2017-03-01

The most important parameters of gas sensors are sensitivity and especially high selectivity to specific chemical species. To improve these parameters we developed sensor structures based on layered semiconducting oxides, namely CuO/Cu2O, CuO:Zn/Cu2O:Zn, NiO/ZnO. In this work, the ZnO/CuxO (where x = 1, 2) bi-layer heterostructure were grown via a simple synthesis from chemical solution (SCS) at relatively low temperatures (< 95 °C), representing a combination of layered n-type and p-type semiconducting oxides which are widely used as sensing material for gas sensors. The main advantages of the developed device structures are given by simplicity of the synthesis and technological cost-efficiency. Structural investigations showed high crystallinity of synthesized layers confirming the presence of zinc oxide nanostructures on the surface of the copper oxide film deposited on glass substrate. Structural changes in morphology of grown nanostructures induced by post-grown thermal annealing were observed by scanning electron microscopy (SEM) investigations, and were studied in detail. The influence of thermal annealing type on the optical properties was also investigated. As an example of practical applications, the ZnO/CuxO bi-layer heterojunctions and ZnO/CuO/Cu2O three-layered structures were integrated into sensor structures and were tested to different types of reducing gases at different operating temperatures (OPT), showing promising results for fabrication of selective gas sensors.

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

PubMed

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

2017-09-01

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

Investigation of the 66Zn(p,2pn) 64Cu and 68Zn(p,x) 64Cu nuclear processes up to 100 MeV: Production of 64Cu

NASA Astrophysics Data System (ADS)

Szelecsényi, F.; Steyn, G. F.; Kovács, Z.; Vermeulen, C.; van der Meulen, N. P.; Dolley, S. G.; van der Walt, T. N.; Suzuki, K.; Mukai, K.

2005-11-01

Cross-sections of the 66Zn(p,2pn)64Cu and 68Zn(p,x)64Cu nuclear processes were measured on highly enriched zinc targets using the stacked-foil activation technique up to 100 MeV. The new cross-sections were compared to literature data. The optimum energy range for production of 64Cu was found to be 70 → 35 MeV on 66Zn and 37 → 20 MeV on 68Zn. The thick-target yields were determined as 777 MBq/μAh (21.0 mCi/μAh) and 185 MBq/μAh (5.0 mCi/μAh), respectively. The yields of the longer-lived contaminant copper radioisotopes (i.e. 61Cu when using 66Zn as target material and both 61Cu and 67Cu in the case of 68Zn target material) were also calculated. The results obtained from the present study indicate that both reactions are suited for the production of 64Cu at a medium energy cyclotron. The optimum energy ranges are also complementary therefore the potential to utilize tandem targetry exists.

Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

NASA Astrophysics Data System (ADS)

Bigalke, Moritz; Weyer, Stefan; Kobza, Jozef; Wilcke, Wolfgang

2010-12-01

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ 65Cu, δ 66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g -1 Cu and 2084 μg g -1 Zn in the organic horizons. The δ 65Cu values varied little (-0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ 66Zn IRMM values were isotopically lighter in ash (-0.41‰) and organic horizons (-0.85‰ to -0.47‰) than in bedrock (-0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ 66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ 66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ 66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources

Aided phytoextraction of Cu, Pb, Zn, and As in copper-contaminated soils with tobacco and sunflower in crop rotation: Mobility and phytoavailability assessment.

PubMed

Hattab-Hambli, Nour; Motelica-Heino, Mikael; Mench, Michel

2016-02-01

Copper-contaminated soils were managed with aided phytoextraction in 31 field plots at a former wood preservation site, using a single incorporation of compost (OM) and dolomitic limestone (DL) followed by a crop rotation with tobacco and sunflower. Six amended plots, with increasing total soil Cu, and one unamended plot were selected together with a control uncontaminated plot. The mobility and phytoavailability of Cu, Zn, Cr and As were investigated after 2 and 3 years in soil samples collected in these eight plots. Total Cu, Zn, Cr and As concentrations were determined in the soil pore water (SPW) and available soil Cu and Zn fractions by DGT. The Cu, Zn, Cr and As phytoavailability was characterized by growing dwarf beans on potted soils and determining the biomass of their plant parts and their foliar ionome. Total Cu concentrations in the SPW increased with total soil Cu. Total Cu, Zn, Cr and As concentrations in the SPW decreased in year 3 as compared to year 2, likely due to annual shoot removals by the plants and the lixiviation. Available soil Cu and Zn fractions also declined in year 3. The Cu, Zn, Cr and As phytoavailability, assessed by their concentration and mineral mass in the primary leaves of beans, was reduced in year 3. Copyright © 2015 Elsevier Ltd. All rights reserved.

Toxicity of nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata.

PubMed

Aruoja, Villem; Dubourguier, Henri-Charles; Kasemets, Kaja; Kahru, Anne

2009-02-01

Toxicities of ZnO, TiO2 and CuO nanoparticles to Pseudokirchneriella subcapitata were determined using OECD 201 algal growth inhibition test taking in account potential shading of light. The results showed that the shading effect by nanoparticles was negligible. ZnO nanoparticles were most toxic followed by nano CuO and nano TiO2. The toxicities of bulk and nano ZnO particles were both similar to that of ZnSO4 (72 h EC50 approximately 0.04 mg Zn/l). Thus, in this low concentration range the toxicity was attributed solely to solubilized Zn2+ ions. Bulk TiO2 (EC50=35.9 mg Ti/l) and bulk CuO (EC50=11.55 mg Cu/l) were less toxic than their nano formulations (EC50=5.83 mg Ti/l and 0.71 mg Cu/l). NOEC (no-observed-effect-concentrations) that may be used for risk assessment purposes for bulk and nano ZnO did not differ (approximately 0.02 mg Zn/l). NOEC for nano CuO was 0.42 mg Cu/l and for bulk CuO 8.03 mg Cu/l. For nano TiO2 the NOEC was 0.98 mg Ti/l and for bulk TiO2 10.1 mg Ti/l. Nano TiO2 formed characteristic aggregates entrapping algal cells that may contribute to the toxic effect of nano TiO2 to algae. At 72 h EC50 values of nano CuO and CuO, 25% of copper from nano CuO was bioavailable and only 0.18% of copper from bulk CuO. Thus, according to recombinant bacterial and yeast Cu-sensors, copper from nano CuO was 141-fold more bioavailable than from bulk CuO. Also, toxic effects of Cu oxides to algae were due to bioavailable copper ions. To our knowledge, this is one of the first systematic studies on effects of metal oxide nanoparticles on algal growth and the first describing toxic effects of nano CuO towards algae.

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

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

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts

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

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.

The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al 2O 3) catalysts for carbon dioxide (CO 2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. Here, we report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO andmore » allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. These results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.« less

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts

DOE PAGES

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.; ...

2017-03-23

The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al 2O 3) catalysts for carbon dioxide (CO 2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. Here, we report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO andmore » allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. These results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.« less

IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer

DOE PAGES

Schumann, Julia; Kröhnert, Jutta; Frei, Elias; ...

2017-08-28

Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm -1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Zn δ+–CO. The presence of not completely reduced Cu δ+–CO speciesmore » cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm -1 due to nano-structured Cu 0–CO and CO adsorbed on highly defective Cu 0, respectively, indicate that the coverage of metallic copper is not complete.« less

IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer

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

Schumann, Julia; Kröhnert, Jutta; Frei, Elias

Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm -1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Zn δ+–CO. The presence of not completely reduced Cu δ+–CO speciesmore » cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm -1 due to nano-structured Cu 0–CO and CO adsorbed on highly defective Cu 0, respectively, indicate that the coverage of metallic copper is not complete.« less

Assessments of serum copper and zinc concentration, and the Cu/Zn ratio determination in patients with multidrug resistant pulmonary tuberculosis (MDR-TB) in Côte d'Ivoire.

PubMed

Bahi, Gnogbo Alexis; Boyvin, Lydie; Méité, Souleymane; M'Boh, Gervais Melaine; Yeo, Kadjowely; N'Guessan, Kouassi Raymond; Bidié, Alain Dit Philippe; Djaman, Allico Joseph

2017-04-11

In Côte d'Ivoire, multidrug-resistant tuberculosis (MDR-TB) is a serious public health problem with a prevalence estimated at 2.5% in 2006. Zinc and copper are essential Trace element needed to strengthen the immune system and also useful in the fight against tuberculosis. The Cu / Zn ratio is a good indicator of oxidative stress. The principal aim of this study was to evaluate the serum concentration of some trace element and determine the Cu / Zn ratio in patients with multidrug resistant pulmonary tuberculosis (MDR-TB) before and after second line treatment of TB. Blood samples were obtained from 100 MDR-TB patients after confirmation of their status through the microscopic and molecular diagnosis of resistance to Isoniazid and Rifampicin by GeneXpert. The concentration level of zinc and copper were determined using flame air / acetylene atomic absorption spectrometer (AAS) Type Varian Spectr AA-20 Victoria, Australlia. A significant decrease in zinc levels (P < 0.05) and an increased Cu / Zn ratio (P < 0.05) was observed in MDR-TB patients compared to controls TB free. During treatment a significant reduction in Cu / Zn ratio (P < 0.05) was observed compared to the initial result. The decrease in serum zinc level and the high Cu / Zn ratio could explain the immune system dysfunction and the high level of oxidative stress in patients with MDR-TB. Therefore the evaluation of the zinc and copper status could represent essential parameters in monitoring of TB second line treatment for better treatment management.

Copper-zinc-superoxide dismutase (CuZnSOD), an antioxidant gene from seahorse (Hippocampus abdominalis); molecular cloning, sequence characterization, antioxidant activity and potential peroxidation function of its recombinant protein.

PubMed

Perera, N C N; Godahewa, G I; Lee, Jehee

2016-10-01

Copper-zinc-superoxide dismutase (CuZnSOD) from Hippocampus abdominalis (HaCuZnSOD) is a metalloenzyme which belongs to the ubiquitous family of SODs. Here, we determined the characteristic structural features of HaCuZnSOD, analyzed its evolutionary relationships, and identified its potential immune responses and biological functions in relation to antioxidant defense mechanisms in the seahorse. The gene had a 5' untranslated region (UTR) of 67 bp, a coding sequence of 465 bp and a 3' UTR of 313 bp. The putative peptide consists of 154 amino acids. HaCuZnSOD had a predicted molecular mass of 15.94 kDa and a theoretical pI value of 5.73, which is favorable for copper binding activity. In silico analysis revealed that HaCuZnSOD had a prominent Cu-Zn_superoxide_dismutase domain, two Cu/Zn signature sequences, a putative N-glycosylation site, and several active sites including Cu(2+) and Zn(2+) binding sites. The three dimensional structure indicated a β-sheet barrel with 8 β-sheets and two short α-helical regions. Multiple alignment analyses revealed many conserved regions and active sites among its orthologs. The highest amino acid identity to HaCuZnSOD was found in Siniperca chuatsi (87.4%), while Maylandia zebra shared a close relationship in the phylogenetic analysis. Functional assays were performed to assess the antioxidant, biophysical and biochemical properties of overexpressed recombinant (r) HaCuZnSOD. A xanthine/XOD assay gave optimum results at pH 9 and 25 °C indicating these may be the best conditions for its antioxidant action in the seahorse. An MTT assay and flow cytometry confirmed that rHaCuZnSOD showed peroxidase activity in the presence of HCO3(-). In all the functional assays, the level of antioxidant activity of rHaCuZnSOD was concentration dependent; metal ion supplementation also increased its activity. The highest mRNA expressional level of HaCuZnSOD was found in blood. Temporal assessment under pathological stress showed a delay

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Deep donor state of the copper acceptor as a source of green luminescence in ZnO

NASA Astrophysics Data System (ADS)

Lyons, J. L.; Alkauskas, A.; Janotti, A.; Van de Walle, C. G.

2017-07-01

Copper impurities have long been linked with green luminescence (GL) in ZnO. Copper is known to introduce an acceptor level close to the conduction band of ZnO, and the GL has conventionally been attributed to transitions involving an excited state which localizes holes on neighboring oxygen atoms. To date, a theoretical description of the optical properties of such deep centers has been difficult to achieve due to the limitations of functionals in the density functional theory. Here, we employ a screened hybrid density functional to calculate the properties of Cu in ZnO. In agreement with the experiment, we find that CuZn features an acceptor level near the conduction band of ZnO. However, we find that CuZn also gives rise to a deep donor level 0.46 eV above the valence band of ZnO; the calculated optical transitions involving this state agree well with the GL observed in ZnO:Cu.

The Megavirus Chilensis Cu,Zn-Superoxide Dismutase: the First Viral Structure of a Typical Cellular Copper Chaperone-Independent Hyperstable Dimeric Enzyme

PubMed Central

Lartigue, Audrey; Burlat, Bénédicte; Coutard, Bruno; Chaspoul, Florence; Claverie, Jean-Michel

2014-01-01

ABSTRACT Giant viruses able to replicate in Acanthamoeba castellanii penetrate their host through phagocytosis. After capsid opening, a fusion between the internal membranes of the virion and the phagocytic vacuole triggers the transfer in the cytoplasm of the viral DNA together with the DNA repair enzymes and the transcription machinery present in the particles. In addition, the proteome analysis of purified mimivirus virions revealed the presence of many enzymes meant to resist oxidative stress and conserved in the Mimiviridae. Megavirus chilensis encodes a predicted copper, zinc superoxide dismutase (Cu,Zn-SOD), an enzyme known to detoxify reactive oxygen species released in the course of host defense reactions. While it was thought that the metal ions are required for the formation of the active-site lid and dimer stabilization, megavirus chilensis SOD forms a very stable metal-free dimer. We used electron paramagnetic resonance (EPR) analysis and activity measurements to show that the supplementation of the bacterial culture with copper and zinc during the recombinant expression of Mg277 is sufficient to restore a fully active holoenzyme. These results demonstrate that the viral enzyme's activation is independent of a chaperone both for disulfide bridge formation and for copper incorporation and suggest that its assembly may not be as regulated as that of its cellular counterparts. A SOD protein is encoded by a variety of DNA viruses but is absent from mimivirus. As in poxviruses, the enzyme might be dispensable when the virus infects Acanthamoeba cells but may allow megavirus chilensis to infect a broad range of eukaryotic hosts. IMPORTANCE Mimiviridae are giant viruses encoding more than 1,000 proteins. The virion particles are loaded with proteins used by the virus to resist the vacuole's oxidative stress. The megavirus chilensis virion contains a predicted copper, zinc superoxide dismutase (Cu,Zn-SOD). The corresponding gene is present in some megavirus

(Zn,H)-codoped copper oxide nanoparticles via pulsed laser ablation on Cu-Zn alloy in water

PubMed Central

2012-01-01

Nanosized (5 to 10 nm) amorphous and crystalline nanocondensates, i.e., metallic α-phase of Zn-Cu alloy in face-centered cubic structure and (Zn,H)-codoped cuprite (Cu2O) with high-pressure-favored close-packed sublattice, were formed by pulsed laser ablation on bulk Cu65Zn35 in water and characterized by X-ray/electron diffractions and optical spectroscopy. The as-fabricated hybrid nanocondensates are darkish and showed photoluminescence in the whole visible region. Further dwelling of such nanocondensates in water caused progressive formation of a rice-like assembly of (Zn,H)-codoped tenorite (CuO) nanoparticles with (001), (100), and {111} preferred orientations, (111) tilt boundary, yellowish color, and minimum bandgap narrowing down to ca. 2.7 eV for potential photocatalytic applications. PMID:22647312

A New Test of Copper and Zinc Abundances in Late-Type Stars Using Cu II and Zn II lines in the Near-Ultraviolet

NASA Astrophysics Data System (ADS)

Roederer, Ian

2017-08-01

The copper (Cu, Z = 29) and zinc (Zn, Z = 30) abundances found in late-type stars provide critical constraints on models that predict the yields of massive star supernovae, hypernovae, Type Ia supernovae, and AGB stars, which are essential ingredients in Galactic chemical evolution models. Furthermore, Zn is commonly used to compare the abundance of iron-group elements in the gas phase in high-redshift DLA systems with metallicities in Local Group stars. It is thus important that the observational Cu and Zn abundances in stars are correct. My proposed archive study will address this issue by using archive STIS spectra of 14 stars to provide the first systematic observational tests of non-LTE calculations of Cu and Zn line formation in late-type stars. The non-LTE calculations predict that all LTE [Cu/Fe] abundance ratios presently found in the literature are systematically lower than the true ratios found in stars. The non-LTE calculations for Zn predict that the LTE values in the literature may be systematically overestimated in low-metallicity stars. The LTE abundances of Cu and Zn are derived from Cu I and Zn I lines. The key advance enabled by the use of NUV spectra is the detection of several lines of Cu II and Zn II, which cannot be detected in the optical or infrared. Cu II and Zn II are largely immune to non-LTE effects in the atmospheres of late-type stars. The metallicities of the 14 stars with NUV spectra span -2.6 < [Fe/H] < -0.1, which covers the range of most Cu and Zn abundances reported in the literature. The proposed study will allow me to test the non-LTE calculations and calibrate the stellar abundances.

Cyclotron production of {sup 61}Cu using natural Zn and enriched {sup 64}Zn targets

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

Asad, A. H.; Smith, S. V.; Chan, S.

2012-12-19

Copper-61 ({sup 61}Cu) shares with {sup 64}Cu certain advantages for PET diagnostic imaging, but has a shorter half-life (3.4hr vs. 12.7hr) and a greater probability of positron production per disintegration (61% vs. 17.9%). One important application is for in vivo imaging of hypoxic tissue. In this study {sup 61}Cu was produced using the {sup 64}Zn(p,{alpha}){sup 61}Cu reaction on natural Zn or enriched {sup 64}Zn targets. The enriched {sup 64}Zn (99.82%) was electroplated onto high purity gold or silver foils or onto thin Al discs. A typical target bombardment used 30{mu}A; at 11.7, 14.5 or 17.6MeV over 30-60min. The {sup 61}Cumore » (radiochemical purity of >95%) was separated using a combination of cation and anion exchange columns. The {sup 64}Zn target material was recovered after each run, for re-use. In a direct comparison with enriched {sup 64}Zn-target results, {sup 61}Cu production using the cheaper {sup nat}Zn target proved to be an effective alternative.« less

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-05-01

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

Selenium, zinc, copper, Cu/Zn ratio and total antioxidant status in the serum of vitiligo patients treated by narrow-band ultraviolet-B phototherapy.

PubMed

Wacewicz, Marta; Socha, Katarzyna; Soroczyńska, Jolanta; Niczyporuk, Marek; Aleksiejczuk, Piotr; Ostrowska, Jolanta; Borawska, Maria H

2018-03-01

Vitiligo is a chronic, depigmenting skin disorder, whose pathogenesis is still unknown. Narrow band ultraviolet-B (NB-UVB) is now one of the most widely used treatment of vitiligo. It was suggested that trace elements may play a role in pathogenesis of vitiligo. The aim of this study was to estimate the concentration of selenium (Se), zinc (Zn), copper (Cu) and Cu/Zn ratio as well as total antioxidant status (TAS) in the serum of patients with vitiligo. We assessed 50 patients with vitiligo and 58 healthy controls. Serum levels of Se, Zn and Cu were determined by the atomic absorption spectrometry method, and the Cu/Zn ratio was also calculated. TAS in serum was measured spectrophotometrically. Serum concentration of Se in patients with vitiligo before and after phototherapy was significantly lower as compared to the control group. Zn level in the serum of patients decreased significantly after phototherapy. We observed higher Cu/Zn ratio (p < .05) in examined patients than in the control group and after NB-UVB. We have found decrease in TAS in the serum of vitiligo patients after NB-UVB. The current study showed some disturbances in the serum levels of trace elements and total antioxidant status in vitiligo patients.

Comparison of Cu2+ and Zn2+ thermalcatalyst in treating diazo dye

NASA Astrophysics Data System (ADS)

Lau, Y. Y.; Wong, Y. S.; Ong, S. A.; Lutpi, N. A.; Ho, L. N.

2018-05-01

This research demonstrates the comparison between copper (II) sulphate (CuSO4) and zinc oxide (ZnO) as thermalcatalysts in thermolysis process for the treatment of diazo reactive black 5 (RB 5) wastewater. CuSO4 was found to be the most effective thermalcatalyst in comparison to ZnO. The color removal efficiency of RB 5 catalysed by CuSO4 and ZnO were 91.55 % at pH 9.5 and 7.36 % at pH 2, respectively. From the UV-Vis wavelength scan, CuSO4 catalyst is able to cleave the molecular structure bonding more efficiently compared to ZnO. ZnO which only show a slight decay on the main chemical network strands: azo bond, naphthalene and benzene rings whereas CuSO4 catalyst is able to fragment azo bond and naphthalene more effectively. The degradation reactions of CuSO4 and ZnO as thermalcatalysts in thermolysis process were compared.

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 .

Improved sensitivity of polychlorinated-biphenyl-orientated porous-ZnO surface photovoltage sensors from chemisorption-formed ZnO-CuPc composites

PubMed Central

Li, Mingtao; Meng, Guowen; Huang, Qing; Zhang, Shile

2014-01-01

We report a new mechanism for the enhancement of porous-ZnO surface photovoltage (SPV) response to polychlorinated biphenyls (PCBs, a notorious class of persistent organic pollutants as global environmental hazard) based on copper phthalocyanine (CuPc) chemisorptive bonding on porous-ZnO. A new ZnO-CuPc composite is formed on the porous-ZnO surface due to the interaction between the surface ZnO and CuPc, with its valence band (VB) energy level being higher than that of the pristine porous-ZnO. So that the efficiency of the photogenerated-electron transfer from the composite VB to the adjacent ZnO's surface states is drastically increased due to the reduced energy gap between the transition states. As a result, the sensitivity of the PCB-orientated SPV sensor is much improved by showing amplified variation of the SPV-signals perturbed by PCBs adsorbed on the ZnO-CuPc@porous-ZnO sensitive material. PMID:24594662

Substitution of Li for Cu in Cu2ZnSnS4: Toward Wide Band Gap Absorbers with Low Cation Disorder for Thin Film Solar Cells.

PubMed

Lafond, A; Guillot-Deudon, C; Vidal, J; Paris, M; La, C; Jobic, S

2017-03-06

The substitution of lithium for copper in Cu 2 ZnSnS 4 (CZTS) has been experimentally and theoretically investigated. Formally, the (Cu 1-x Li x )ZnSnS 4 system exhibits two well-defined solid solutions. Indeed, single crystal structural analyses demonstrate that the low (x < 0.4) and high (x > 0.6) lithium-content compounds adopt the kesterite structure and the wurtz-kesterite structure, respectively. For x between 0.4 and 0.6, the two aforementioned structure types coexist. Moreover, 119 Sn NMR analyses carried out on a (Cu 0.7 Li 0.3 ) 2 ZnSnS 4 sample clearly indicate that lithium replaces copper preferentially on two of the three available 2-fold crystallographic sites commonly occupied by Cu and Zn in disordered kesterite. Furthermore, the observed individual lines in the NMR spectrum suggest that the propensity of Cu and Zn atoms to be randomly distributed over the 2c and 2d crystallographic sites is lowered when lithium is partially substituted for copper. Additionally, the first-principles calculations provide insights into the arrangement of Li atoms as a function of the Cu/Zn disorder and its effect on the structural (lattice parameters) and optical properties of CZTS (band gap evolution). Those calculations agree with the experimental observations and account for the evolutions of the unit cell parameters as well as for the increase of band gap when the Li-content increases. The calculation of the formation enthalpy of point defect unambiguously indicates that Li modifies the Cu/Zn disorder in a manner similar to the change of Cu/Zn disorder induced by Ag alloying. Overall, it was found that Li alloying is a versatile way of tuning the optoelectronic properties of CZTS making it a good candidate as wide band gap materials for the top cells of tandem solar cells.

The optoelectronic properties and role of Cu concentration on the structural and electrical properties of Cu doped ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Omri, K.; Bettaibi, A.; Khirouni, K.; El Mir, L.

2018-05-01

In the current study, we synthesized a Cu-doped ZnO (CZO) nanoparticles material using a sol-gel method with different doping concentrations of Cu (0, 2, 3 and 4 at.%). The control of the Cu concentration on structural, electrical and optical properties of CZO nanoparticles was investigated in detail. The XRD analysis of the CZO nanoparticles reveals the formation of ZnO hexagonal wurtzite structure for all samples which confirm the incorporation of Cu2+ ions into the ZnO lattice by substitution. Furthermore, CZO nanoparticles showed a small red shift of absorption band with the incorporation of Cu from 0 to 4 at.%; i.e. a decreased band gap value from 3.34 eV to 3.27 eV with increasing of Cu doping content. The frequency dispersion of the electric conductivity were studied using the Jonscher universal power law, according to relation σ(ω) = σDC + A ωs(T). Alternative current conductivity increases with increasing Cu content in spite of the decrease the activation energy with copper loading. It was found that the conductivity reached its maximum value for critical Cu concentration of 3 at.%. The frequency relaxation phenomenon was also investigated and all results were discussed in term of the copper doping concentration.

Zinc and copper behaviour at the soil-river interface: New insights by Zn and Cu isotopes in the organic-rich Rio Negro basin

NASA Astrophysics Data System (ADS)

Guinoiseau, Damien; Gélabert, Alexandre; Allard, Thierry; Louvat, Pascale; Moreira-Turcq, Patricia; Benedetti, Marc F.

2017-09-01

The complex behaviour of Zn and Cu at the soil-river interface was investigated in soil and riverine water samples from the Rio Negro basin, a secondary tributary of the Rio Amazonas, using their stable isotope compositions. This acidic and organic river drains two types of intensely weathered terrains: podzols in its upstream part, and lateritic soils downstream. Bulk soil particles, suspended particulate matter (SPM) as well as colloidal fractions were sampled across the whole basin during low and high water stages. In the basin, Zn and Cu are mostly exported from lateritic soils and transported by organic colloids where significant losses are observed in the downstream part of the river. The use of δ66Zn and δ65Cu measurements reveals distinct stories for these two metals in suspended sediments and colloids. In the colloids, the constant δ66Zncoll across the basin is induced by the same weak association mode between Zn and organic ligands, regardless of the origin of the water. By contrast, in SPM, the speciation of Zn and thus δ66ZnSPM differ according to the type of drained soils. Zn is associated with organic complexes in particles exported with water draining podzol whereas Zn2+ is incorporated in the structure of the remaining kaolinite clays in lateritic output. The stronger reactivity of Cu than Zn with organic ligands induces its complete complexation. Copper is controlled by refractory particulate organic matter (POM) and by reactive colloidal organic matter; the latter being enriched in 65Cu due to stronger binding interactions than in POM. While the Cu content remains constant in the upstream part of the Rio Negro, downstream, the decrease of SPM and colloidal Cu fluxes is associated with a constant δ65CuSPM and with an increase of δ65Cucoll at the Rio Negro outlet. Geochemical mass balance modelling, based on SPM, Cu and Zn fluxes in SPM and their associated isotopic signatures, confirms distinct host phases for Zn and Cu, and identifies the

Cryoprotective role of organic Zn and Cu supplementation in goats (Capra hircus) diet.

PubMed

Arangasamy, Arunachalam; Krishnaiah, Mayasula Venkata; Manohar, Narasimhaiah; Selvaraju, Sellappan; Rani, Guvvala Pushpa; Soren, Nira Manik; Reddy, Ippala Janardhan; Ravindra, Janivara Parameshwaraiah

2018-04-01

The current study focused on cryopreservation and assessment of characters of post-thaw semen of indigenous Osmanabadi bucks maintained with standard diet, supplemented with different concentrations of organic zinc (Zn), copper (Cu) or in combination, for a period of 180 days. The different doses of organic Zn and Cu were fed per kg DM basis, Zn groups (low: Zn20, medium: Zn40 and high: Zn60), Cu groups: (low: Cu12.5, medium: Cu25 and high: Cu37.5) and combination of Zn + Cu groups (low: Zn20 + Cu12.5, medium: Zn40 + Cu25 and high: Zn60 + Cu37.5) respectively. The control group bucks were maintained mainly on the basal diet without any additional mineral supplementation. Two hundred and forty (240) semen samples were collected from 40 bucks aged 11 months, through electro ejaculator method, processed and analysed for sperm quality parameters both at pre freeze and post-thaw stage. The semen samples were diluted in Tris egg yolk extender, cooled and equilibrated for 4 h at 5 °C, cryopreserved using programmable freezer (PLANER Kryo 360-1.7) and stored at -196 °C. The organic trace minerals (Zn, Cu and Zn + Cu) protected the spermatozoa against the cryoinjury and maintained higher post-thaw semen parameters except in high Zn group. Additional feeding of organic Cu and Zn to bucks had a protective role and resulted in higher sperm liveability, plasma membrane and acrosome integrities, motility and velocity and reduced oxidative stress in supplemented goats (P < 0.05). Copyright © 2018 Elsevier Inc. All rights reserved.

Syntheses, structures, and properties of imidazolate-bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) dinuclear complexes of a single macrocyclic ligand with two hydroxyethyl pendants.

PubMed

Li, Dongfeng; Li, Shuan; Yang, Dexi; Yu, Jiuhong; Huang, Jin; Li, Yizhi; Tang, Wenxia

2003-09-22

The imidazolate-bridged homodinuclear Cu(II)-Cu(II) complex, [(CuimCu)L]ClO(4).0.5H(2)O (1), and heterodinuclear Cu(II)-Zn(II) complex, [(CuimZnL(-)(2H))(CuimZnL(-)(H))](ClO(4))(3) (2), of a single macrocyclic ligand with two hydroxyethyl pendants, L (L = 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene), have been synthesized as possible models for copper-zinc superoxide dismutase (Cu(2),Zn(2)-SOD). Their crystal structures analyzed by X-ray diffraction methods have shown that the structures of the two complexes are markedly different. Complex 1 crystallizes in the orthorhombic system, containing an imidazolate-bridged dicopper(II) [Cu-im-Cu](3+) core, in which the two copper(II) ions are pentacoordinated by virtue of an N4O environment with a Cu.Cu distance of 5.999(2) A, adopting the geometry of distorted trigonal bipyramid and tetragonal pyramid, respectively. Complex 2 crystallizes in the triclinic system, containing two similar Cu-im-Zn cores in the asymmetric unit, in which both the Cu(II) and Zn(II) ions are pentacoordinated in a distorted trigonal bipyramid geometry, with the Cu.Zn distance of 5.950(1)/5.939(1) A, respectively. Interestingly, the macrocyclic ligand with two arms possesses a chairlike (anti) conformation in complex 1, but a boatlike (syn) conformation in complex 2. Magnetic measurements and ESR spectroscopy of complex 1 have revealed the presence of an antiferromagnetic exchange interaction between the two Cu(II) ions. The ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 2 displayed a typical signal for mononuclear trigonal bipyramidal Cu(II) complexes. From pH-dependent ESR and electronic spectroscopic studies, the imidazolate bridges in the two complexes have been found to be stable over broad pH ranges. The cyclic voltammograms of the two complexes have been investigated. Both of the two complexes can catalyze the dismutation of superoxide and show rather high activity.

New influence factor inducing difficulty in selective flotation separation of Cu-Zn mixed sulfide minerals

NASA Astrophysics Data System (ADS)

Deng, Jiu-shuai; Mao, Ying-bo; Wen, Shu-ming; Liu, Jian; Xian, Yong-jun; Feng, Qi-cheng

2015-02-01

Selective flotation separation of Cu-Zn mixed sulfides has been proven to be difficult. Thus far, researchers have found no satisfactory way to separate Cu-Zn mixed sulfides by selective flotation, mainly because of the complex surface and interface interaction mechanisms in the flotation solution. Undesired activation occurs between copper ions and the sphalerite surfaces. In addition to recycled water and mineral dissolution, ancient fluids in the minerals are observed to be a new source of metal ions. In this study, significant amounts of ancient fluids were found to exist in Cu-Zn sulfide and gangue minerals, mostly as gas-liquid fluid inclusions. The concentration of copper ions released from the ancient fluids reached 1.02 × 10-6 mol/L, whereas, in the cases of sphalerite and quartz, this concentration was 0.62 × 10-6 mol/L and 0.44 × 10-6 mol/L, respectively. As a result, the ancient fluid is a significant source of copper ions compared to mineral dissolution under the same experimental conditions, which promotes the unwanted activation of sphalerite. Therefore, the ancient fluid is considered to be a new factor that affects the selective flotation separation of Cu-Zn mixed sulfide ores.

Soil solution dynamics of Cu and Zn in a Cu- and Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction.

PubMed

Luo, Y M; Yan, W D; Christie, P

2001-01-01

A pot experiment was conducted to study soil solution dynamics of Cu and Zn in a Cu/Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction. A slightly acid sandy loam was amended with Cu and Zn (as nitrates) either singly or in combination (100 mg Cu and 150 mg Zn kg(-1) soil) and was then gamma-irradiated (10 kGy). Unamended and unirradiated controls were included, and spring barley (Hordeum vulgare L. cv. Forrester) was grown for 50 days. Soil solution samples obtained using soil moisture samplers immediately before transplantation and every ten days thereafter were used directly for determination of Cu, Zn, pH and absorbance at 360 nm (A360). Cu and Zn concentrations in the solution of metal-polluted soil changed with time and were affected by gamma-irradiation and metal interaction. gamma-Irradiation raised soil solution Cu substantially but generally decreased soil solution Zn. These trends were consistent with increased dissolved organic matter (A360) and solution pH after gamma-irradiation. Combined addition of Cu and Zn usually gave higher soil solution concentrations of Cu or Zn compared with single addition of Cu or Zn in gamma-irradiated and non-irradiated soils, indicating an interaction between Cu and Zn. Cu would have been organically complexed and consequently maintained a relatively high concentration in the soil solution under higher pH conditions. Zn tends to occur mainly as free ion forms in the soil solution and is therefore sensitive to changes in pH. The extent to which gamma-irradiation and metal interaction affected solubility and bioavailability of Cu and Zn was a function of time during plant growth. Studies on soil solution metal dynamics provide very useful information for understanding metal mobility and bioavailability.

The Effect of (Ag, Ni, Zn)-Addition on the Thermoelectric Properties of Copper Aluminate

PubMed Central

Yanagiya, Shun-ichi; Van Nong, Ngo; Xu, Jianxiao; Pryds, Nini

2010-01-01

Polycrystalline bulk copper aluminate Cu1-x-yAgxByAlO2 with B = Ni or Zn were prepared by spark plasma sintering and subsequent thermal treatment. The influence of partial substitution of Ag, Ni and Zn for Cu-sites in CuAlO2 on the high temperature thermoelectric properties has been studied. The addition of Ag and Zn was found to enhance the formation of CuAlO2 phase and to increase the electrical conductivity. The addition of Ag or Ag and Ni on the other hand decreases the electrical conductivity. The highest power factor of 1.26 × 10-4 W/mK2 was obtained for the addition of Ag and Zn at 1,060 K, indicating a significant improvement compared with the non-doped CuAlO2 sample.

Electrodeposition of Zn and Cu-Zn alloy from ZnO/CuO precursors in deep eutectic solvent

NASA Astrophysics Data System (ADS)

Xie, Xueliang; Zou, Xingli; Lu, Xionggang; Lu, Changyuan; Cheng, Hongwei; Xu, Qian; Zhou, Zhongfu

2016-11-01

The electrodeposition of Zn and Cu-Zn alloy has been investigated in choline chloride (ChCl)/urea (1:2 molar ratio) based deep eutectic solvent (DES). Cyclic voltammetry study demonstrates that the reduction of Zn(II) to Zn is a diffusion-controlled quasi-reversible, one-step, two electrons transfer process. Chronoamperometric investigation indicates that the electrodeposition of Zn on a Cu electrode typically involves three-dimensional instantaneous nucleation with diffusion-controlled growth process. Micro/nanostructured Zn films can be obtained by controlling the electrodeposition potential and temperature. The electrodeposited Zn crystals preferentially orient parallel to the (101) plane. The Zn films electrodeposited under more positive potentials and low temperatures exhibit improved corrosion resistance in 3 wt% NaCl solution. In addition, Cu-Zn alloy films have also been electrodeposited directly from CuO-ZnO precursors in ChCl/urea-based DES. The XRD analysis indicates that the phase composition of the electrodeposited Cu-Zn alloy depends on the electrodeposition potential.

Transduced human copper chaperone for Cu,Zn-SOD (PEP-1-CCS) protects against neuronal cell death.

PubMed

Choi, Soo Hyun; Kim, Dae Won; Kim, So Young; An, Jae Jin; Lee, Sun Hwa; Choi, Hee Soon; Sohn, Eun Jung; Hwang, Seok-Il; Won, Moo Ho; Kang, Tae-Cheon; Kwon, Hyung Joo; Kang, Jung Hoon; Cho, Sung-Woo; Park, Jinseu; Eum, Won Sik; Choi, Soo Young

2005-12-31

Reactive oxygen species (ROS) contribute to the development of various human diseases. Cu,Zn-superoxide dismutase (SOD) is one of the major means by which cells counteract the deleterious effects of ROS. SOD activity is dependent upon bound copper ions supplied by its partner metallochaperone protein, copper chaperone for SOD (CCS). In the present study, we investigated the protective effects of PEP-1-CCS against neuronal cell death and ischemic insults. When PEP-1-CCS was added to the culture medium of neuronal cells, it rapidly entered the cells and protected them against paraquat-induced cell death. Moreover, transduced PEP-1-CCS markedly increased endogenous SOD activity in the cells. Immunohistochemical analysis revealed that it prevented neuronal cell death in the hippocampus in response to transient forebrain ischemia. These results suggest that CCS is essential to activate SOD, and that transduction of PEP-1-CCS provides a potential strategy for therapeutic delivery in various human diseases including stroke related to SOD or ROS.

Application of 67Cu Produced by 68Zn(n,n'p+d)67Cu to Biodistribution Study in Tumor-Bearing Mice

NASA Astrophysics Data System (ADS)

Sugo, Yumi; Hashimoto, Kazuyuki; Kawabata, Masako; Saeki, Hideya; Sato, Shunichi; Tsukada, Kazuaki; Nagai, Yasuki

2017-02-01

67Cu produced by the 68Zn(n,n'p+d)67Cu reaction was used for the first time to determine the biodistribution of 67CuCl2 in colorectal tumor-bearing mice. A high uptake of 67Cu was observed in the tumor as well as in the liver and kidney, which are the major organs for copper metabolism. The result showing 67Cu accumulation in the tumor suggests that 67CuCl2 can be a potential radionuclide agent for cancer radiotherapy. It should also encourage further studies on the therapeutic effect on small animals using an increased dose of 67Cu produced by the 68Zn(n,n'p+d)67Cu reaction using presently available intense neutrons.

Effect of copper doping sol-gel ZnO thin films: physical properties and sensitivity to ethanol vapor

NASA Astrophysics Data System (ADS)

Boukaous, Chahra; Benhaoua, Boubaker; Telia, Azzedine; Ghanem, Salah

2017-10-01

In the present paper, the effect of copper doping ZnO thin films, deposited using a sol-gel dip-coating technique, on the structural, optical and ethanol vapor-sensing properties, was investigated. The range of the doping content is 0 wt. %-5 wt. % Cu/Zn and the films’ properties were studied using x-ray diffraction, scanning electron microscopy and a UV-vis spectrophotometer. The obtained results indicated that undoped and copper-doped zinc oxide thin films have polycrystalline wurtzite structure with (1 0 1) preferred orientation. All samples have a smooth and dense structure free of pinholes. A decrease in the band gap with Cu concentration in the ZnO network was observed. The influence of the dopant on ethanol vapor-sensing properties shows an increase in the film sensitivity to the ethanol vapor within the Cu concentration.

The crystalline structure of copper phthalocyanine films on ZnO(1100).

PubMed

Cruickshank, Amy C; Dotzler, Christian J; Din, Salahud; Heutz, Sandrine; Toney, Michael F; Ryan, Mary P

2012-09-05

The structure of copper phthalocyanine (CuPc) thin films (5-100 nm) deposited on single-crystal ZnO(1100) substrates by organic molecular beam deposition was determined from grazing-incidence X-ray diffraction reciprocal space maps. The crystal structure was identified as the metastable polymorph α-CuPc, but the molecular stacking was found to vary depending on the film thickness: for thin films, a herringbone arrangement was observed, whereas for films thicker than 10 nm, coexistence of both the herringbone and brickstone arrangements was found. We propose a modified structure for the herringbone phase with a larger monoclinic β angle, which leads to intrastack Cu-Cu distances closer to those in the brickstone phase. This structural basis enables an understanding of the functional properties (e.g., light absorption and charge transport) of (opto)electronic devices fabricated from CuPc/ZnO hybrid systems.

Structural, chemical and optical evaluation of Cu-doped ZnO nanoparticles synthesized by an aqueous solution method

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

Iribarren, A., E-mail: augusto@imre.oc.uh.cu; Hernández-Rodríguez, E.; Maqueira, L.

Highlights: • Cu-doped ZnO nanoparticles obtained by chemical synthesis. • Substitutional or interstitial Cu into ZnO lead specific structural, chemical, and optical changes. • Incorporation efficiency of Cu atoms in ZnO as a function of the Cu concentration in the precursor dissolution. - Abstract: In this work a study of ZnO and Cu-doped ZnO nanoparticles obtained by chemical synthesis in aqueous media was carried out. Structural analysis gave the dominant presence of wurtzite ZnO phase forming a solid solution Zn{sub 1−x}Cu{sub x}O. For high Cu doping CuO phase is also present. For low Cu concentration the lattice shrinks due tomore » Cu atoms substitute Zn atoms. For high Cu concentration the lattice enlarges due to predominance of interstitial Cu. From elemental analysis we determined and analyzed the incorporation efficiency of Cu atoms in Zn{sub 1−x}Cu{sub x}O as a function of the Cu concentration in the precursor dissolution. Combining structural and chemical results we described the Cu/Zn precursor concentrations r{sub w} in which the solid solution of Cu in ZnO is predominant. In the region located at r{sub w} ≈ 0.2–0.3 it is no longer valid. For Cu/Zn precursor concentration r{sub w} > 0.3 interstitial Cu dominates, and some amount of copper oxide appears. As the Cu concentration increases, the effective size of nanoparticles decreases. Photoluminescence (PL) measurements of the Cu-doped ZnO nanoparticles were carried out and analyzed.« less

Unoccupied states in Cu and Zn octaethyl-porphyrin and phthalocyanine.

PubMed

Cook, Peter L; Yang, Wanli; Liu, Xiaosong; García-Lastra, Juan María; Rubio, Angel; Himpsel, F J

2011-05-28

Copper and zinc phthalocyanines and porphyrins are used in organic light emitting diodes and dye-sensitized solar cells. Using near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the Cu 2p and Zn 2p edges, the unoccupied valence states at the Cu and Zn atoms are probed and decomposed into 3d and 4s contributions with the help of density functional calculations. A comparison with the N 1s edge provides the 2p states of the N atoms surrounding the metal, and a comparison with inverse photoemission provides a combined density of states. © 2011 American Institute of Physics

Effects of Cu(2+) and Zn(2+) on growth and physiological characteristics of green algae, Cladophora.

PubMed

Cao, De-ju; Xie, Pan-pan; Deng, Juan-wei; Zhang, Hui-min; Ma, Ru-xiao; Liu, Cheng; Liu, Ren-jing; Liang, Yue-gan; Li, Hao; Shi, Xiao-dong

2015-11-01

Effects of various concentrations of Cu(2+) and Zn(2+) (0.0, 0.1, 0.25, 0.5, or 1.0 mg/L) on the growth, malondialdehyde (MDA), the intracellular calcium, and physiological characteristics of green algae, Cladophora, were investigated. Low Zn(2+) concentrations accelerated the growth of Cladophora, whereas Zn(2+) concentration increases to 0.25 mg/L inhibited its growth. Cu(2+) greatly influences Cladophora growth. The photosynthesis of Cladophora decreased under Zn(2+) and Cu(2+) stress. Cu(2+) and Zn(2+) treatment affected the content of total soluble sugar in Cladophora and has small increases in its protein content. Zn(2+) induced the intracellular calcium release, and copper induced the intracellular calcium increases in Cladophora. Exposure to Cu(2+) and Zn(2+) induces MDA in Cladophora. The stress concent of Cu(2+) was strictly correlated with the total soluble sugar content, Chla+Chlb, and MDA in Cladophora, and the stress concent of Zn(2+) was strictly correlated with the relative growth rate (RGR) and MDA of Cladophora.

The effect of copper and silver on the properties of Au-ZnO catalyst and its activity in glycerol oxidation

NASA Astrophysics Data System (ADS)

Kaskow, Iveta; Decyk, Piotr; Sobczak, Izabela

2018-06-01

The goal of this work was to use ZnO as a support for gold and copper (Au-Cu system) or gold and silver (Au-Ag system) and comparison of the effect of copper and silver on the properties of gold and its activity in glycerol oxidation with oxygen in the liquid phase. The samples prepared were fully characterized by XRD, TEM techniques and UV-vis, XPS, ESR spectroscopic methods. It was found that the introduction of copper and silver changed the electronic state of gold loaded on ZnO by the electron transfer between metals. Three different metallic gold species were identified in calcined catalysts: (Au°)δ- (Au-ZnO), (Au°)η- (AuCu-ZnO) and (Au°)γ- (AuAg-ZnO), where δ-,η-,γ- indicate a different partial negative charge on metallic gold and γ > δ > η. The results showed that (Au°)η- centers (metallic gold with the lowest negative charge) formed on AuCu-ZnO were the most active in glycerol oxidation. The increase in the negative charge on metallic gold loaded on AuAg-ZnO reduced the gold activity in silver containing sample. The glyceric acid adsorption and desorption rate influenced the selectivity of the catalysts.

P-Type Transparent Cu-Alloyed ZnS Deposited at Room Temperature

DOE PAGES

Woods-Robinson, Rachel; Cooper, Jason K.; Xu, Xiaojie; ...

2016-03-16

All transparent conducting materials (TCMs) of technological practicality are n-type; the inferior conductivity of p-type TCMs has limited their adoption. Additionally, many relatively high-performing p-type TCMs require synthesis temperatures > 400 °C. Here, room-temperature pulsed laser deposition of copper-alloyed zinc sulfide (Cu x Zn 1- x S) thin films (0 ≤ x ≤ 0.75) is reported. For 0.09 ≤ x ≤ 0.35, Cu x Zn 1- x S has high p-type conductivity, up to 42 S cm -1 at x = 0.30, with an optical band gap tunable from ≈3.0–3.3 eV and transparency, averaged over the visible, of 50%–71% formore » 200–250 nm thick films. In this range, synchrotron X-ray and electron diffraction reveal a nanocrystalline ZnS structure. Secondary crystalline Cu y S phases are not observed, and at higher Cu concentrations, x > 0.45, films are amorphous and poorly conducting. Furthermore, within the TCM regime, the conductivity is temperature independent, indicating degenerate hole conduction. A decrease in lattice parameter with Cu content suggests that the hole conduction is due to substitutional incorporation of Cu onto Zn sites. This hole-conducting phase is embedded in a less conducting amorphous Cu y S, which dominates at higher Cu concentrations. Finally, the combination of high hole conductivity and optical transparency for the peak conductivity Cu x Zn 1- x S films is among the best reported to date for a room temperature deposited p-type TCM.« less

Tracing contamination sources in soils with Cu and Zn isotopic ratios.

PubMed

Fekiacova, Z; Cornu, S; Pichat, S

2015-06-01

Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of copper doping on the photocatalytic activity of ZnO thin films prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Saidani, T.; Zaabat, M.; Aida, M. S.; Boudine, B.

2015-12-01

In the present work, we prepared undoped and copper doped ZnO thin films by the sol-gel dip coating method on glass substrates from zinc acetate dissolved in a solution of ethanol. The objective of our work is to study the effect of Cu doping with different concentrations on structural, morphological, optical properties and photocatalytic activity of ZnO thin films. For this purpose, we have used XRD to study the structural properties, and AFM to determine the morphology of the surface of the ZnO thin films. The optical properties and the photocatalytic degradation of the films were examined by UV-visibles spectrophotometer. The Tauc method was used to estimate the optical band gap. The XRD spectra indicated that the films have an hexagonal wurtzite structure, which gradually deteriorated with increasing Cu concentration. The results showed that the incorporation of Cu decreases the crystallite size. The AFM study showed that an increase of the concentration of Cu causes the decrease of the surface roughness, which passes from 20.2 for Un-doped ZnO to 12.16 nm for doped ZnO 5 wt% Cu. Optical measurements have shown that all the deposited films show good optical transmittance (77%-92%) in the visible region and increases the optical gap with increasing Cu concentration. The presence of copper from 1% to 5 wt% in the ZnO thin films is found to decelerate the photocatalytic process.

Synthesis, characterization and crystal structure of a 1D thiocyanato bridged [Cu(en)2Zn(NCS)4]ṡH2O. Comparison of the three structures with the same [Cu(en)2Zn(NCS)4] unit - different in structural terms

NASA Astrophysics Data System (ADS)

Wrzeszcz, Grzegorz; Muzioł, Tadeusz M.; Tereba, Natalia

2015-03-01

In this paper we report the synthesis method and the structure of a one-dimensional thiocyanato bridged heterometallic compound, [Cu(en)2Zn(NCS)4]ṡH2O (1). Moreover, we compare the structure of (1) with the previously described structures of [Cu(en)2Zn(NCS)4]ṡ0.5H2O (2) and [Cu(en)2Zn(NCS)4]ṡCH3CN (3) Pryma et al. (2003) [7]. The compound (1) has been characterized by thermal decomposition, IR, Vis and EPR spectra, and magnetic studies. Structure has been determined by X-ray analysis. Described coordination polymer crystallizes in the orthorhombic Cmcm space group with a = 12.414(2), b = 10.3276(14), c = 14.967(2) Å, α = β = γ = 90°, V = 1918.8(5) Å3 and Z = 4. Each distorted tetrahedral zinc(II) centre (with N-bonded NCS-) links two tetragonally distorted octahedral copper(II) centres by two end-to-end thiocyanato bridges and vice versa forming a zigzag type of CuZn chain. The structures of (1), (2) and (3) differ in crystallographic system, space group and/or CuZn chain type as well as in details. Variable temperature magnetic susceptibility measurements show very weak antiferromagnetic interactions between the paramagnetic copper(II) ions for compound (1).

The potentiation effect makes the difference: non-toxic concentrations of ZnO nanoparticles enhance Cu nanoparticle toxicity in vitro.

PubMed

Li, Lingxiangyu; Fernández-Cruz, María Luisa; Connolly, Mona; Conde, Estefanía; Fernández, Marta; Schuster, Michael; Navas, José María

2015-02-01

Here we examined whether the addition of a non-toxic concentration (6.25 μg/mL) of zinc oxide nanoparticles (ZnONPs: 19, 35 and 57 nm, respectively) modulates the cytotoxicity of copper nanoparticles (CuNPs, 63 nm in size) in the human hepatoma cell line HepG2. The cytotoxic effect of CuNPs on HepG2 cells was markedly enhanced by the ZnONPs, the largest ZnONPs causing the highest increase in toxicity. However, CuNPs cytotoxicity was not affected by co-incubation with medium containing only zinc ions, indicating the increase in toxicity might be attributed to the particle form of ZnONPs. Transmission electron microscopy (TEM) revealed the presence of CuNPs and ZnONPs inside the cells co-exposed to both types of NP and outflow of cytoplasm through the damaged cell membrane. Inductively coupled plasma mass spectrometry (ICP-MS) determined an increase in the concentration of zinc and a decrease in that of copper in co-exposed cells. On the basis of these results, we propose that accumulation of large numbers of ZnONPs in the cells alters cellular membranes and the cytotoxicity of CuNPs is increased. Copyright © 2014 Elsevier B.V. All rights reserved.

[Changes in bio-availability of immobilized Cu and Zn bound to phosphate in contaminated soils with different nutrient addition].

PubMed

Xu, Ming-Gang; Zhang, Qian; Sun, Nan; Shen, Hua-Ping; Zhang, Wen-Ju

2009-07-15

Bio-availability of Cu and Zn fixed by phosphate in contaminated soils with application of nutrients were measured by pot experiment. It was simulated for the third national standardization of copper and zinc polluted soils by adding copper and zinc nitrate into red and paddy soils, respectively and together. Phosphate amendment was added to the soils to fix Cu and Zn, then added KCl and NH4Cl or K2SO4 and (NH4)2SO4 fertilizers following to plant Ryegrass, which was harvested after 40 d. Available Cu/Zn content in soils and biomass, Cu/Zn content in the shoot of Ryegrass were determined. Results showed that, compared with no nutrient application, adding KCl and NH4 Cl/K2SO4 and (NH4)2SO4 to polluted red and paddy soils increased the available Cu and Zn content in red soil significantly. The increasing order was KCl and NH4 Cl > K2SO4 and (NH4)2SO4. Especially in single Zn polluted red soil, the available Zn content increased by 133.4% in maximum. Although adding K2SO4 and (NH4)2SO4 could promote the growth of Ryegrass on red soil, and the largest increasing was up to 22.2%, it increased Cu and Zn content in the shoot of Ryegrass for 21.5%-112.6% remarkably. These nutrient effects on available Cu and Zn were not significantly in paddy soil. It was suggested that application of nitrogen and potassium fertilizers to soils could change the bioavailability of Cu/Zn. So it is necessary to take full account of the nutrient influence to the heavy metal stability which fixed by phosphate in contaminated soils when consider contaminated soils remediation by fertilization.

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties

NASA Astrophysics Data System (ADS)

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-01

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications

Ferromagnetic mechanism of (Co, Cu)-codoped ZnO films with different Co concentrations investigated by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Yuan, Huan; Du, Xiaosong; Xu, Ming

2016-05-01

Cobalt/copper-codoped ZnO nanoparticles, synthesized with different Co concentrations by a sol-gel method using ethanol as solvent, were studied via XPS. Hexagonal wurtzite structure was found in all samples, with no evidence of any secondary phase. The average crystallite size of the samples was around 20-30 nm, altered significantly with increasing Co concentration. Copper ions and Cobalt ions are indeed substituted into the ZnO lattice at the Zn2+ site, as shown by XRD and XPS. Further studies showed dramatic changes of Cu valence from +2 to +1 as the Co concentration level exceeds 1%, accompanied by a blue-shift of the optical bandgap from 3.01 to 3.13 eV. Ferromagnetism of the Co-doped Zn0.95Cu0.05O thin films was observed and found to be tunable - a phenomenon associated with the valence state of the Cu ions and the existence of some defects like oxygen vacancies in the films.

Influence of copper composition on mechanical properties of biodegradable material Mg-Zn-Cu for orthopedic application

NASA Astrophysics Data System (ADS)

Purniawan, A.; Maulidiah, H. M.; Purwaningsih, H.

2018-04-01

Implant is usually used as a treatment of bone fracture. At the moment, non-biodegradable implants is still widely employed in this application. Non-biodegradable implant requires re-surgery to retrieve implants that are installed in the body. It increase the cost and it is painful for the patient itself. In order to solve the problem, Mg-based biodegradable metals is developing so that the material will be compatible with body and gradually degrade in patient's body. However, magnesium has several disadvantages such as high degradation rates and low mechanical properties when compared to the mechanical properties of natural bone. Therefore, it is necessary to add elements into the magnesium alloy. In this research, copper (Cu) was alloyed in Mg alloy based biodegradable material. In addition, Cu is not only strengthening the structure but also for supporting element for the immune system, antibacterial and antifungal. The purpose of this research is to improve mechanical properties of Mg-based biodegradable material using Cu alloying. Powder metallurgy method was used to fabricate the device. The variation used in this research is the composition of Cu (0.5, 1, and 1.5% Cu). The porosity test was performed using apparent porosity test, compressive test and hardness test to know the mechanical properties of the alloy, and the weightless test to find out the material degradation rate. Based on the results can be conclude that Mg-Zn-Cu alloy material with 1% Cu composition is the most suitable specimen to be applied as a candidate for orthopedic devices material with hardness value is 393.6 MPa. Also obtained the value of the compressive test is 153 MPa.

Synthesis and structural characterization of ZnO and CuO nanoparticles supported mesoporous silica SBA-15

NASA Astrophysics Data System (ADS)

El-Nahhal, Issa M.; Salem, Jamil K.; Selmane, Mohamed; Kodeh, Fawzi S.; Ebtihan, Heba A.

2017-01-01

Zinc oxide (ZnO) and copper oxide (CuO) nanoparticles were loaded into mesoporous silica SBA-15 by post-synthesis and direct methods. The structural properties were characterized using wide and small angle X-ray diffraction (WXRD & SXRD), X-ray photoelectron spectroscopy (XPS) and N2-adsorption desorption (BET). The WXRD showed that, the loaded zinc and copper oxides were present in crystalline forms (impregnation). The mesoporosity properties of SBA-15 silica were well maintained even after the introduction of metal oxide nanoparticles. BET analysis indicate that the impregnated and condensed ZnO and CuO supported SBA-15 nanocomposites have a lower surface area than that of its parent SBA-15.

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties.

PubMed

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-02

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.

Cs promoted oxidation of Zn and CuZn surfaces: a combined experimental and theoretical study

NASA Astrophysics Data System (ADS)

Chaturvedi, Sanjay; Rodriguez, JoséA.; Hrbek, Jan

1997-07-01

The interaction of O 2 with Zn, {Cs}/{Zn} and {Cs}/{CuZn} surfaces was investigated using photoemission and ab initio self-consistent-field (SCF) calculations. On zinc films, the sticking probability of O 2 is extremely low (10 -3-10 -2), and O 2 exposures in the range of 10 3 to 10 4 langmuirs are necessary to produce a significant adsorption of oxygen and the transformation of metallic zinc into zinc oxide. The presence of sub monolayer coverages of cesium enhances the oxidation rate of zinc by 2-3 orders of magnitude. In the {Cs}/{Zn} system, the alkali atom donates electrons to zinc. This charge transfer facilitates the formation of Zn→O 2 dative bonds and breaking of the OO bond. For the coadsorption of Cs and O 2 on Zn(001), the larger the electron transfer from Zn into the O 2 (1 πg) orbitals, the bigger the adsorption energy of the molecule and the elongation of the OO bond. In general, cesium does not promote the oxidation of copper. In the {Cs}/{CuZn} system, copper withdraws electrons from zinc. The presence of copper in the {Cs}/{CuZn} system inhibits the oxidation of the Zn component compared with the {Cs}/{Zn} system by lowering the electron density on the Zn atoms. After exposing the {Cs}/{CuZn} system to O 2, zinc is oxidized at a rate that is larger than that found for clean CuZn surfaces and smaller than seen in {Cs}/{Zn} surfaces. Molecular hydrogen is found to have no effect on oxidized Cu, Zn and CuZn films. However, atomic hydrogen reduces ZnO to metallic zinc and CuO to Cu 2O. In the oxidized CuZn alloy, CuO is reduced first followed by the reduction of ZnO. A comparison of the behavior of O 2/Cs/Zn and H 2O/Cs/Zn systems shows that while O 2 causes severe oxidation of Cs promoted Zn surfaces, H 2O has little or no effect.

Evaluation of Serum Levels of Zinc, Copper, Iron, and Zinc/Copper Ratio in Cutaneous Leishmaniasis

PubMed Central

Pourfallah, F; Javadian, S; Zamani, Z; Saghiri, R; Sadeghi, S; Zarea, B; Faiaz, Sh; Mirkhani, F; Fatemi, N

2009-01-01

Background: The purpose of this study was to evaluate the levels of zinc (Zn), copper (Cu), iron (Fe) and zinc/ copper ratio in the serum of patients with cutaneous leishmaniasis in Qom Province, center of Iran. Methods: Serum levels of zinc and copper were determined by flame atomic absorption spectrophotometer and serum iron concentration was measured by using an Auto Analyzer. The study group consisted of 60 patients with cutaneous leishmaniasis and the control group of 100 healthy volunteers from the same area who were not exposed to cutaneous leishmaniasis. Result: There were no statistically significant differences in age and body mass index between the two groups. Serum Zn (P< 0.001) and Fe (P< 0.05) levels were lower in patients with cutaneous leishmaniasis than the control group. We also found serum Cu concentration (P< 0.05) in the patient group was significantly higher than that of the control group. However, zinc/ copper ratio (P< 0.001) was lower in patients with cutaneous leishmaniasis than in the control group. Conclusion: Our data indicated that Zn/Cu ratio was significantly lower in patients with CL as compared to the controls. Earlier reports suggest that, this ratio imbalance could be a useful marker for immune dysfunction in leishmaniasis. There was also strong association of Zn, Cu and Fe with CL. It suggests the use of blood zinc, copper, iron concentration and the copper/zinc ratio (Zn/Cu), as a means for estimating the prognosis of CL. PMID:22808376

Synthesis of ZnO-CuO/MCM-48 photocatalyst for the degradation of organic pollutions.

PubMed

Duan, Yongzheng; Shen, Yulian

2017-07-01

The photocatalytic properties of ZnO-CuO catalysts supported on siliceous MCM-48 (Mobil Composition of Matter No. 48) for the degradation of organic pollutions such as methylene blue and salicylic acid under UV light irradiation were investigated. These catalysts were prepared by impregnation of MCM-48 with a mixed aqueous solution of copper acetate and zinc acetate. X-ray diffraction, N 2 -physisorption, high resolution transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and photoluminescence were used to characterize these samples. Results from characterizations showed that the addition of ZnO to CuO/MCM-48 could markedly improve the photocatalytic degradation properties. The enhanced photocatalytic behaviors of ZnO-CuO/MCM-48 may be due to the formation of p-n heterojunctions between ZnO and CuO, resulting in the effective separation of photogenerated electron-hole pairs. Moreover, the photocatalysts were easily recovered and reused for five cycles without considerable loss of activity.

Co(II) derivatives of Cu,Zn-superoxide dismutase with the cobalt bound in the place of copper. A new spectroscopic tool for the study of the active site.

PubMed

Desideri, A; Cocco, D; Calabrese, L; Rotilio, G

1984-03-29

Co(II) derivatives of Cu,Zn-superoxide dismutase having cobalt substituted for the copper (Co,Zn-superoxide dismutase and Co,Co-superoxide dismutase) were studied by optical and EPR spectroscopy. EPR and electronic absorption spectra of Co,Zn-superoxide dismutase are sensitive to solvent perturbation, and in particular to the presence of phosphate. This behaviour suggests that cobalt in Co,Zn-superoxide dismutase is open to solvent access, at variance with the Co(II) of the Cu,Co-superoxide dismutase, which is substituted for the Zn. Phosphate binding as monitored by optical titration is dependent on pH with an apparent pKa = 8.2. The absorption spectrum of Co,Zn-superoxide dismutase in water has three weak bands in the visible region (epsilon = 75 M-1 X cm-1 at 456 nm; epsilon = 90 M-1 X cm-1 at 520 nm; epsilon = 70 M-1 X cm-1 at 600 nm) and three bands in the near infrared region, at 790 nm (epsilon = 18 M-1 X cm-1), 916 nm (epsilon = 27 M-1 X cm-1) and 1045 nm (epsilon = 25 M-1 X cm-1). This spectrum is indicative of five-coordinate geometry. In the presence of phosphate, three bands are still present in the visible region but they have higher intensity (epsilon = 225 M-1 X cm-1 at 544 nm; epsilon = 315 M-1 X cm-1 at 575 nm; epsilon = 330 M-1 X cm-1 at 603 nm), whilst the lowest wavelength band in the near infrared region is at much lower energy, 1060 nm (epsilon = 44 M-1 X cm-1). The latter property suggests a tetrahedral coordination around the Co(II) centre. Addition of 1 equivalent of CN- gives rise to a stable Co(II) low-spin intermediate, which is characterized by an EPR spectrum with a highly rhombic line shape. Formation of this CN- complex was found to require more cyanide equivalents in the case of the phosphate adduct, suggesting that binding of phosphate may inhibit binding of other anions. Titration of the Co,Co-derivative with CN- provided evidence for magnetic interaction between the two metal centres. These results substantiate the contention

Salts affect the interaction of ZnO or CuO nanoparticles with wheat.

PubMed

Stewart, Jacob; Hansen, Trevor; McLean, Joan E; McManus, Paul; Das, Siddhartha; Britt, David W; Anderson, Anne J; Dimkpa, Christian O

2015-09-01

Exposure to nanoparticles (NPs) that release metals with potential phytotoxicity could pose problems in agriculture. The authors of the present study used growth in a model growth matrix, sand, to examine the influence of 5 mmol/kg of Na, K, or Ca (added as Cl salts) and root exudates on transformation and changes to the bioactivity of copper(II) oxide (CuO) and zinc oxide (ZnO) NPs on wheat. These salt levels are found in saline agricultural soils. After 14 d of seedling growth, particles with crystallinity typical of CuO or ZnO remained in the aqueous fraction from the sand; particles had negative surface charges that differed with NP type and salt, but salt did not alter particle agglomeration. Reduction in shoot and root elongation and lateral root induction by ZnO NPs were mitigated by all salts. However, whereas Na and K promoted Zn loading into shoots, Ca reduced loading, suggesting that competition with Zn ions for uptake occurred. With CuO NPs, plant growth and loading was modified equally by all salts, consistent with major interaction with the plant with CuO rather than Cu ions. Thus, for both NPs, loading into plant tissues was not solely dependent on ion solubility. These findings indicated that salts in agricultural soils could modify the phytotoxicity of NPs. © 2015 SETAC.

Integration of ZnO and CuO nanowires into a thermoelectric module

PubMed Central

Dalola, Simone; Faglia, Guido; Comini, Elisabetta; Ferroni, Matteo; Soldano, Caterina; Ferrari, Vittorio; Sberveglieri, Giorgio

2014-01-01

Summary Zinc oxide (ZnO, n-type) and copper oxide (CuO, p-type) nanowires have been synthesized and preliminarily investigated as innovative materials for the fabrication of a proof-of-concept thermoelectric device. The Seebeck coefficients, electrical conductivity and thermoelectric power factors (TPF) of both semiconductor materials have been determined independently using a custom experimental set-up, leading to results in agreement with available literature with potential improvement. Combining bundles of ZnO and CuO nanowires in a series of five thermocouples on alumina leads to a macroscopic prototype of a planar thermoelectric generator (TEG) unit. This demonstrates the possibility of further integration of metal oxide nanostructures into efficient thermoelectric devices. PMID:24991531

Integration of ZnO and CuO nanowires into a thermoelectric module.

PubMed

Zappa, Dario; Dalola, Simone; Faglia, Guido; Comini, Elisabetta; Ferroni, Matteo; Soldano, Caterina; Ferrari, Vittorio; Sberveglieri, Giorgio

2014-01-01

Zinc oxide (ZnO, n-type) and copper oxide (CuO, p-type) nanowires have been synthesized and preliminarily investigated as innovative materials for the fabrication of a proof-of-concept thermoelectric device. The Seebeck coefficients, electrical conductivity and thermoelectric power factors (TPF) of both semiconductor materials have been determined independently using a custom experimental set-up, leading to results in agreement with available literature with potential improvement. Combining bundles of ZnO and CuO nanowires in a series of five thermocouples on alumina leads to a macroscopic prototype of a planar thermoelectric generator (TEG) unit. This demonstrates the possibility of further integration of metal oxide nanostructures into efficient thermoelectric devices.

Concentration of selenium, zinc, copper, Cu/Zn ratio, total antioxidant status and c-reactive protein in the serum of patients with psoriasis treated by narrow-band ultraviolet B phototherapy: A case-control study.

PubMed

Wacewicz, Marta; Socha, Katarzyna; Soroczyńska, Jolanta; Niczyporuk, Marek; Aleksiejczuk, Piotr; Ostrowska, Jolanta; Borawska, Maria H

2017-12-01

Psoriasis is a common, an inflammatory skin disease. Trace elements may play an active role in the pathogenesis of psoriasis. The aim of this study was to estimate the concentration of selenium (Se), zinc (Zn), copper (Cu) and Cu/Zn ratio as well as total antioxidant status (TAS) and c-reactive protein (CRP) in the serum of patients with psoriasis. In this case-control study sixty patients with psoriasis and fifty-eight healthy people were examined. Serum levels of Se, Zn and Cu were determined by atomic absorption spectrometry. Cu/Zn ratio was calculated. TAS was measured spectrophotometrically. CRP was analyzed by immunoturbidimetric method. Clinical activity of psoriasis was evaluated using Psoriasis Area and Severity Index (PASI). Serum concentration of Se in patients with psoriasis (71.89±16.90μg/L) was lower as compared to the control group (79.42±18.97μg/L) and after NB-UVB. Cu level of patients was higher (1.151±0.320mg/L) as compared to controls (1.038±0.336mg/L), but Zn level did not differ. We observed higher Cu/Zn ratio (p<0.05) in examined patients than in the control group and after NB-UVB. We found decrease TAS before and after NB-UVB. CRP levels was found to be normal range. A significant correlation coefficient between CRP and Cu/Zn was observed. The study showed some disturbances in the serum levels of trace elements and TAS in psoriatic patients. Copyright © 2017 The Authors. Published by Elsevier GmbH.. All rights reserved.

Detection of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases in co-evaporated Cu2ZnSnSe4 thin-films

NASA Astrophysics Data System (ADS)

Schwarz, Torsten; Marques, Miguel A. L.; Botti, Silvana; Mousel, Marina; Redinger, Alex; Siebentritt, Susanne; Cojocaru-Mirédin, Oana; Raabe, Dierk; Choi, Pyuck-Pa

2015-10-01

Cu2ZnSnSe4 thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu2ZnSnSe4 and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases. Possible effects of these phases on solar cell performance are discussed.

Surface characterization of ZnO/ZnMn{sub 2}O{sub 4} and Cu/Mn{sub 3}O{sub 4} powders obtained by thermal degradation of heterobimetallic complexes

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

Barrault, Joeel, E-mail: joel.barrault@univ-poitiers.fr; Makhankova, Valeriya G., E-mail: leram@univ.kiev.ua; Khavryuchenko, Oleksiy V.

2012-03-15

From the selective transformation of the heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes with 2,2 Prime -bipyridyl by thermal degradation at relatively low (350 Degree-Sign C) temperature, it was possible to get either well defined spinel ZnMn{sub 2}O{sub 4} over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn{sub 3}O{sub 4}) in a core-shell like structure. Morphology of the powder surface was examined by scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX). Surface composition was determined by X-ray photoelectron spectroscopy (XPS). Specific surface of the powders by nitrogen adsorption was found to be 33{+-}0.2 and 9{+-}0.06more » m{sup 2} g{sup -1} for Zn-Mn and Cu-Mn samples, respectively, which is comparable to those of commercial products. - Graphical abstract: From the selective transformation of heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes, it was possible to get either well defined spinel ZnMn{sub 2}O{sub 4} over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn{sub 3}O{sub 4}) in a core-shell like structure. Highlights: Black-Right-Pointing-Pointer Thermal degradation of heterometallic complexes results in fine disperse particles. Black-Right-Pointing-Pointer Core-shell Cu/Mn{sub 3}O{sub 4} particles are obtained. Black-Right-Pointing-Pointer ZnMn{sub 2}O{sub 4} spinel layer covers ZnO particles.« less

Copper Sensing Function of Drosophila Metal-Responsive Transcription Factor-1 Is Mediated By a Tetranuclear Cu(I) Cluster

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

Chen, X.; Hua, H.; Balamurugan, K.

2009-05-12

Drosophila melanogaster MTF-1 (dMTF-1) is a copper-responsive transcriptional activator that mediates resistance to Cu, as well as Zn and Cd. Here, we characterize a novel cysteine-rich domain which is crucial for sensing excess intracellular copper by dMTF-1. Transgenic flies expressing mutant dMTF-1 containing alanine substitutions of two, four or six cysteine residues within the sequence {sup 547}CNCTNCKCDQTKSCHGGDC{sup 565} are significantly or completely impaired in their ability to protect flies from copper toxicity and fail to up-regulate MtnA (metallothionein) expression in response to excess Cu. In contrast, these flies exhibit wild-type survival in response to copper deprivation thus revealing that themore » cysteine cluster domain is required only for sensing Cu load by dMTF-1. Parallel studies show that the isolated cysteine cluster domain is required to protect a copper-sensitive S. cerevisiae ace1 strain from copper toxicity. Cu(I) ligation by a Cys-rich domain peptide fragment drives the cooperative assembly of a polydentate [Cu{sub 4}-S{sub 6}] cage structure, characterized by a core of trigonally S{sub 3} coordinated Cu(I) ions bound by bridging thiolate ligands. While reminiscent of Cu{sub 4}-L{sub 6} (L = ligand) tetranuclear clusters in copper regulatory transcription factors of yeast, the absence of significant sequence homology is consistent with convergent evolution of a sensing strategy particularly well suited for Cu(I).« less

Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings.

PubMed

Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A H

2015-01-01

Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal.

Comparison of Antibacterial Effects of ZnO and CuO Nanoparticles Coated Brackets against Streptococcus Mutans.

PubMed

Ramazanzadeh, Baratali; Jahanbin, Arezoo; Yaghoubi, Masoud; Shahtahmassbi, Nasser; Ghazvini, Kiarash; Shakeri, Mohammadtaghi; Shafaee, Hooman

2015-09-01

During the orthodontic treatment, microbial plaques may accumulate around the brackets and cause caries, especially in high-risk patients. Finding ways to eliminate this microbial plaque seems to be essential. The aim of this study was to compare the antibacterial effects of nano copper oxide (CuO) and nano zinc oxide (ZnO) coated brackets against Streptococcus mutans (S.mutans) in order to decrease the risk of caries around the orthodontic brackets during the treatment. Sixty brackets were coated with nanoparticles of ZnO (n=20), CuO (n=20) and CuO-ZnO (n=20). Twelve uncoated brackets constituted the control group. The brackets were bonded to the crowns of extracted premolars, sterilized and prepared for antimicrobial tests (S.mutans ATCC35668). The samples taken after 0, 2, 4, 6 and 24 hours were cultured on agar plates. Colonies were counted 24 hours after incubation. One-way ANOVA and Tukey tests were used for statistical analysis. In CuO and CuO-ZnO coated brackets, no colony growth was seen after two hours. Between 0-6 hours, the mean colony counts were not significantly different between the ZnO and the control group (p>0.05). During 6-24 hours, the growth of S.mutans was significantly reduced by ZnO nanoparticles in comparison with the control group (p< 0.001). However, these bacteria were not totally eliminated. CuO and ZnO-CuO nanoparticles coated brackets have better antimicrobial effect on S.mutans than ZnO coated brackets.

Abundant defects and defect clusters in kesterite Cu2ZnSnS4 and Cu2ZnSnSe4

NASA Astrophysics Data System (ADS)

Chen, Shiyou; Wang, Lin-Wang; Walsh, Aron; Gong, Xin-Gao; Wei, Su-Huai

2013-03-01

Cu2ZnSnS4 and Cu2ZnSnSe4 are drawing intensive attention as the light-absorber materials in thin-film solar cells. A large variety of intrinsic defects can be formed in these quaternary semiconductors, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. We will present our first-principles calculation study on a series of intrinsic defects and defect clusters in Cu2ZnSnS4 and Cu2ZnSnSe4, and discuss: (i) strong phase-competition between the kesterites and the coexisting secondary compounds; (ii) the dominant CuZn antisites and Cu vacancies which determine the intrinsic p-type conductivity, and their dependence on the elemental ratios; (iii) the high population of charge-compensated defect clusters (like VCu + ZnCu and 2CuZn + SnZn) and their contribution to non-stoichiometry ; (iv) the deep-level defects which act as recombination centers. Based on the calculation, we will explain the experimental observation that Cu poor and Zn rich conditions give the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu2ZnSn(S,Se)4 cells with high S composition. Supported by NSF of China, JCAP: a U.S. DOE Energy Innovation Hub, Royal Society of U.K. and EPSRC, and U.S. DOE.

Zn II(atsm) is protective in amyotrophic lateral sclerosis model mice via a copper delivery mechanism.

PubMed

McAllum, Erin J; Roberts, Blaine R; Hickey, James L; Dang, Theresa N; Grubman, Alexandra; Donnelly, Paul S; Liddell, Jeffrey R; White, Anthony R; Crouch, Peter J

2015-09-01

Mutations in the metalloprotein Cu,Zn-superoxide dismutase (SOD1) cause approximately 20% of familial cases of amyotrophic lateral sclerosis (ALS), a fatal neurodegenerative disease for which effective therapeutics do not yet exist. Transgenic rodent models based on over-expression of mutant SOD1 have been developed and these have provided opportunity to test new therapeutic strategies and to study the mechanisms of mutant SOD1 toxicity. Although the mechanisms of mutant SOD1 toxicity are yet to be fully elucidated, incorrect or incomplete metallation of SOD1 confers abnormal folding, aggregation and biochemical properties, and improving the metallation state of SOD1 provides a viable therapeutic option. The therapeutic effects of delivering copper (Cu) to mutant SOD1 have been demonstrated recently. The aim of the current study was to determine if delivery of zinc (Zn) to SOD1 was also therapeutic. To investigate this, SOD1G37R mice were treated with the metal complex diacetyl-bis(4-methylthiosemicarbazonato)zinc(II) [Zn(II)(atsm)]. Treatment resulted in an improvement in locomotor function and survival of the mice. However, biochemical analysis of spinal cord tissue collected from the mice revealed that the treatment did not increase overall Zn levels in the spinal cord nor the Zn content of SOD1. In contrast, overall levels of Cu in the spinal cord were elevated in the Zn(II)(atsm)-treated SOD1G37R mice and the Cu content of SOD1 was also elevated. Further experiments demonstrated transmetallation of Zn(II)(atsm) in the presence of Cu to form the Cu-analogue Cu(II)(atsm), indicating that the observed therapeutic effects for Zn(II)(atsm) in SOD1G37R mice may in fact be due to in vivo transmetallation and subsequent delivery of Cu. Copyright © 2015. Published by Elsevier Inc.

Flexibility of the Cu,Zn superoxide dismutase structure investigated at 0.57 GPa.

PubMed

Ascone, Isabella; Savino, Carmelinda; Kahn, Richard; Fourme, Roger

2010-06-01

The 2 A resolution crystal structure of bovine erythrocyte Cu,Zn superoxide dismutase (CuZnSOD) has been determined by X-ray diffraction at high pressure (0.57 GPa) and room temperature. At 0.57 GPa the secondary, tertiary and quaternary structures are similar to other previously determined bovine erythrocyte CuZnSOD structures. Nevertheless, pressure has a localized impact on the atomic coordinates of C(alpha) atoms and on side chains. The compression of the crystal and of the protein backbone is anisotropic. This anisotropy is discussed, taking into account intermolecular contacts and protein conformation. Pressure perturbation highlights the more flexible zones in the protein such as the electrostatic loop. At 0.57 GPa, a global shift of the dimetallic sites in both subunits and changes in the oxidation state of Cu were observed. The flexibility of the electrostatic loop may be useful for the interaction of different metal carriers in the copper-uptake process, whereas the flexibility of the metal sites involved in the activity of the protein could contribute to explaining the ubiquitous character of CuZnSODs, which are found in organisms living in very different conditions, including the deep-sea environment. This work illustrates the potential of combining X-ray crystallography with high pressure to promote and stabilize higher energy conformational substates.

Assessment of the Zinc and Copper Status in Alpaca.

PubMed

Pechová, A; Husáková, T; Pavlata, L; Holasová, M; Hauptmanová, K

2018-02-01

This study was performed with the aim of investigating the concentration of zinc and copper in the blood of healthy alpacas (Vicugna pacos) kept in central Europe and to compare the concentration of Zn and Cu in plasma and in whole blood. A further objective was to evaluate blood Zn and Cu in relation to different micromineral supplementation, age and sex groups of alpacas. A total of 299 alpacas (224 adults and 75 crias) from 18 farms were included in this study. The concentrations of copper and zinc in plasma/whole blood were measured by flame atomic absorption spectrometry. The results of this study show high individual variability in plasma Zn (median 3.54, range 1.56-8.01 μmol/l), whole blood Zn (median 10.01, range 6.23-75.0 μmol/l), plasma Cu (median 7.53, range 2.93-16.41 μmol/l) and whole blood Cu (median 6.33, range 3.02-13.95 μmol/l). Plasma Zn was not significantly influenced by sex, age or feeding group. Whole blood Zn was only significantly higher in females than in males. The intake of Zn in all groups was equal to or higher than the nutritional recommendation. During excessive supplementation, Zn absorption decreased and thus blood Zn did not reflect the higher intake. Only a weak correlation was found (Spearman correlation coefficient r = 0.384; p > 0.01; n = 204) between plasma and whole blood Zn concentrations. Plasma copper concentration was significantly influenced by age, sex and feeding; whole blood Cu by age and feeding. However, neither plasma Cu nor whole blood Cu reflected the intake of the element. We found a close correlation between plasma and blood copper concentrations (Spearman correlation coefficient r = 0.9043; p ≤ 0.01; n = 99). According to our results, copper in plasma or blood is not a good indicator of copper intake.

Structural, morphological, optical and electrical properties of Schottky diodes based on CBD deposited ZnO:Cu nanorods

NASA Astrophysics Data System (ADS)

Mwankemwa, Benard S.; Legodi, Matshisa J.; Mlambo, Mbuso; Nel, Jackie M.; Diale, Mmantsae

2017-07-01

Undoped and copper doped zinc oxide (ZnO) nanorods have been synthesized by a simple chemical bath deposition (CBD) method at a temperature of 90 °C. Structural, morphological, optical and electrical properties of the synthesized ZnO nanorods were found to be dependent on the Cu doping percentage. X-ray diffraction (XRD) patterns revealed strong diffraction peaks of hexagonal wurtzite of ZnO, and no impurity phases from metallic zinc or copper. Scanning electron microscopy (SEM) images showed changes in diameter and shape of nanorods, where by those doped with 2 at.% and 3 at.% aggregated and became compact. Selected area electron diffraction (SAED) patterns indicates high quality, single crystalline wurtzite structure ZnO and intensities of bright spots varied with copper doping concentration. UV-visible absorption peaks of ZnO red shifted with increasing copper doping concentration. Raman studies demonstrated among others, strong and sharp E2 (low) and E2 (high) optical phonon peaks confirming crystal structure of ZnO. Current-voltage measurements based on the gold/ZnO nanorods/ITO showed good rectifying behavior of the Schottky diode. The predicted Schottky barrier height of 0.60 eV was obtained which is not far from the theoretical Schottky-Mott value of 0.80 eV.

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

Divacancy complexes induced by Cu diffusion in Zn-doped GaAs

NASA Astrophysics Data System (ADS)

Elsayed, M.; Krause-Rehberg, R.; Korff, B.; Ratschinski, I.; Leipner, H. S.

2013-08-01

Positron annihilation spectroscopy was applied to investigate the nature and thermal behavior of defects induced by Cu diffusion in Zn-doped p-type GaAs crystals. Cu atoms were intentionally introduced in the GaAs lattice through thermally activated diffusion from a thin Cu capping layer at 1100 °C under defined arsenic vapor pressure. During isochronal annealing of the obtained Cu-diffused GaAs in the temperature range of 450-850 K, vacancy clusters were found to form, grow and finally disappear. We found that annealing at 650 K triggers the formation of divacancies, whereas further increasing in the annealing temperature up to 750 K leads to the formation of divacancy-copper complexes. The observations suggest that the formation of these vacancy-like defects in GaAs is related to the out-diffusion of Cu. Two kinds of acceptors are detected with a concentration of about 1016 - 1017 cm-3, negative ions and arsenic vacancy copper complexes. Transmission electron microscopy showed the presence of voids and Cu precipitates which are not observed by positron measurements. The positron binding energy to shallow traps is estimated using the positron trapping model. Coincidence Doppler broadening spectroscopy showed the presence of Cu in the immediate vicinity of the detected vacancies. Theoretical calculations suggested that the detected defect is VGaVAs-2CuGa.

Simultaneous adsorption and degradation of Zn(2+) and Cu (2+) from wastewaters using nanoscale zero-valent iron impregnated with clays.

PubMed

Shi, Li-Na; Zhou, Yan; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravi

2013-06-01

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu(2+) and Zn(2+) from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu(2+) and Zn(2+) from a aqueous solution containing a 100 mg/l of Cu(2+) and Zn(2+), where 92.9 % Cu(2+) and 58.3 % Zn(2+) were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu(2+) and Zn(2+). A kinetics study indicated that removing Cu(2+) and Zn(2+) with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu(2+)and Zn(2+) on bentonite and the degradation of Cu(2+)and Zn(2+) by nZVI on the bentonite. However, Cu(2+) removal by B-nZVI was reduced rather than adsorption, while Zn(2+) removal was main adsorption. Finally, Cu(2+), Zn(2+), Ni(2+), Pb(2+) and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.

Site-selective XAFS spectroscopy tuned to surface active sites of Cu/ZnO and Cr/SiO2 catalysts.

PubMed

Izumi, Y; Nagamori, H; Kiyotaki, F; Minato, T

2001-03-01

XAFS (X-ray absorption fine structure) spectra were measured by using the fluorescence spectrometer for the emitted X-ray from sample. The chemical shifts between Cu0 and Cu1 and between CrIII and CrVI were evaluated. Tuning the fluorescence spectrometer to each energy, the Cu0 and CuI site-selective XANES for Cu/ZnO catalyst were measured. The first one was similar to the XANES of Cu metal and the second one was the 5 : 5 average of XANES for CuI sites + Cu metal. The population ratio of copper site of the Cu/ZnO catalyst was found to be Cu metal: Cu2O : CuI atomically dispersed on surface = 70(+/-23) : 22(+/-14) : 8(+/-5). Site-selective XANES for CrIII site of Cr/SiO2 catalyst was also studied.

Preparation & characterization of high purity Cu2 ZnSn(SxSe1-x)4 nanoparticles

NASA Astrophysics Data System (ADS)

Negash, Bethlehem G.

Research in thin film solar cells applies novel techniques to synthesize cost effective and highly efficient absorber materials in order to generate electricity directly from solar energy. Of these materials, copper zinc tin sulfoselenide (Cu2ZnSn(SxSe1-x) 4) nanoparticles have shown great promise in solar cell applications due to optimal material properties as well as low cost & relative abundance of materials.1,2 Sulfoselenide nanoparticles have also a broader impact in other industries including electronics3, LED 4, and biomedical research5. Of the many routes of manufacturing these class of semiconductors, colloidal synthesis of Cu 2ZnSn(SxSe1-x)4 offers a scalable, low cost and high-throughput route for manufacturing high efficiency thin-film solar cells. Hydrazine processed Cu2ZnSn(SxSe1-x )4 devices have reached a record power conversion efficiency (PCE) of 12.6%, much higher than the 9.6% reported for physical vapor deposition (PVD) systems.6,7. Despite high efficiencies, wet synthesis of nanoparticles, however, is made more complicated in multi-element, quaternary and quinary systems such as copper zinc tin sulfoselenide (CZTSSe) and copper indium gallium diselenide (CIGSe). One major disadvantage in these systems is growth of the desired quaternary or quinary phase in competition with unwanted binary and ternary phases with low energy of formation.8,9 Moreover, various reaction parameters such as reaction time, temperature, and choice of ligand also affect, chemical as well as physical properties of resulting nanoparticles. Understanding of the formation mechanisms of the particles is necessary in order to address some of these challenges in wet synthesis of CZTSSe nanoparticles. In this study, we investigate synthesis conditions & reaction parameters which yield high purity Cu2ZnSn(SxSe1-x) 4 nanoparticles as well as attempt to understand the growth mechanism of these nanoparticles. This was achieved by manipulating anion precursor preparation routes as

Spectral features and antibacterial properties of Cu-doped ZnO nanoparticles prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Alireza, Samavati; A, F. Ismail; Hadi, Nur; Z, Othaman; M, K. Mustafa

2016-07-01

Zn1-x Cu x O (x = 0.00, 0.01, 0.03, and 0.05) nanoparticles are synthesized via the sol-gel technique using gelatin and nitrate precursors. The impact of copper concentration on the structural, optical, and antibacterial properties of these nanoparticles is demonstrated. Powder x-ray diffraction investigations have illustrated the organized Cu doping into ZnO nanoparticles up to Cu concentration of 5% (x = 0.05). However, the peak corresponding to CuO for x = 0.01 is not distinguishable. The images of field emission scanning electron microscopy demonstrate the existence of a nearly spherical shape with a size in the range of 30-52 nm. Doping Cu creates the Cu-O-Zn on the surface and results in a decrease in the crystallite size. Photoluminescence and absorption spectra display that doping Cu causes an increment in the energy band gap. The antibacterial activities of the nanoparticles are examined against Escherichia coli (Gram negative bacteria) cultures using optical density at 600 nm and a comparison of the size of inhibition zone diameter. It is found that both pure and doped ZnO nanoparticles indicate appropriate antibacterial activity which rises with Cu doping. Project supported by the Universiti Teknologi Malaysia (UTM) (Grant No. R. J1300000.7809.4F626). Dr. Samavati is thankful to RMC for postdoctoral grants.

Copper exposure induces oxidative injury, disturbs the antioxidant system and changes the Nrf2/ARE (CuZnSOD) signaling in the fish brain: protective effects of myo-inositol.

PubMed

Jiang, Wei-Dan; Liu, Yang; Hu, Kai; Jiang, Jun; Li, Shu-Hong; Feng, Lin; Zhou, Xiao-Qiu

2014-10-01

The brain is the center of the nervous system in all vertebrates, and homeostasis of the brain is crucial for fish survival. Copper (Cu) is essential for normal cellular processes in most eukaryotic organisms but is toxic in excess. Although Cu is indicated as a potent neurotoxicant, information regarding its threat to fish brain and underlying mechanisms is still scarce. In accordance, the objective of this study was to assess the effects and the potential mechanism of Cu toxicity by evaluating brain oxidative status, the enzymatic and mRNA levels of antioxidant genes, as well as the Nrf2/ARE signaling in the brain of fish after Cu exposure. The protective effects of myo-inositol (MI) against subsequent Cu exposure were also investigated. The results indicate that induction of oxidative stress by Cu is shown by increases in brain ROS production, lipid peroxidation and protein oxidation, which are accompanied by depletions of antioxidants, including total superoxide dismutase (T-SOD), CuZnSOD, glutathione-S-transferase (GST) and glutathione reductase (GR) activities and glutathione (GSH) content. Cu exposure increased the catalase (CAT) and glutathione peroxidase (GPx) activities. Further molecular results showed that Cu exposure up-regulated CuZnSOD, GPx1a and GR mRNA levels, suggesting an adaptive mechanism against stress. Moreover, Cu exposure increased fish brain Nrf2 nuclear accumulation and increased its ability of binding to ARE (CuZnSOD), which supported the increased CuZnSOD mRNA levels. In addition, Cu exposure caused increases of the expression of the Nrf2, Maf G1 (rather than Maf G2 gene) and PKCd genes, suggesting that de novo synthesis of those factors is required for the protracted induction of such antioxidant genes. However, the modulation of Keap1a (rather than Keap1b) of fish brain under Cu exposure might be used to turn off of the signaling cascade and avoid harmful effects. Interestingly, pre-treatment of fish with MI prevented the fish brain

Metallochaperone for Cu,Zn-superoxide dismutase (CCS) protein but not mRNA is higher in organs from copper-deficient mice and rats.

PubMed

Prohaska, Joseph R; Broderius, Margaret; Brokate, Bruce

2003-09-15

Cu,Zn-superoxide dismutase (SOD1) is an abundant metalloenzyme important in scavenging superoxide ions. Cu-deficient rats and mice have lower SOD1 activity and protein, possibly because apo-SOD1 is degraded faster than holo-SOD1. SOD1 interacts with and requires its metallochaperone CCS for donating copper. We produced dietary Cu deficiency in rodents to determine if the reduction in SOD1 was related to the level of its specific metallochaperone CCS. CCS levels determined by immunoblot were 2- to 3-fold higher in liver, heart, kidney, and brain from male Cu-deficient rats and mice under a variety of conditions. CCS was also higher in livers of Cu-deficient dams. Interestingly, CCS levels in brain of Cu-deficient mice were also higher even though SOD1 activity and protein were not altered, suggesting that the rise in CCS is correlated with altered Cu status rather than a direct result of lower SOD1. A DNA probe specific for rat CCS detected a single transcript by Northern blot hybridization with liver RNA. CCS mRNA levels in mouse and rat liver were not altered by dietary treatment. These results suggest a posttranscriptional mechanism for higher CCS protein when Cu is limiting in the cell, perhaps due to slower protein turnover. Elevation in CCS level is one of the most dramatic alterations in Cu binding proteins accompanying Cu deficiency and may be useful to assess Cu status.

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

PubMed

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

2015-03-21

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

Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings

PubMed Central

Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A. H.

2015-01-01

Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal. PMID

Estimated daily intake of Fe, Cu, Ca and Zn through common cereals in Tehran, Iran.

PubMed

Kashian, S; Fathivand, A A

2015-06-01

This paper presents the findings of study undertaken to estimate the dietary intake of iron (Fe), copper (Cu), calcium (Ca) and zinc (Zn) through common cereals in Tehran, Iran. 100 samples of rice, wheat and barley were collected from various brands between August and October 2013. The samples were analyzed performing instrumental neutron activation analysis (INAA). The dietary intake for adults was estimated by a total cereal study. Calculations were carried out on the basis of the reported adults' average food consumption rate data. The total daily intake estimated in mgd(-1) for Tehran population were 3.6 (Fe), 10.2 (Zn), 0.3 (Cu) and 234.5 (Ca). Wheat showed the highest contribution to Zn, Cu and Ca intakes. Furthermore, intakes were compared with recommended dietary allowance (RDA). Zn total intake (10.2mgd(-1)) was comparable with RDA values for males (11mgd(-1)) and was higher than recommended value for females (8mgd(-1)). The intakes of other studied elements were below the respective RDAs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Gene transcription patterns and energy reserves in Daphnia magna show no nanoparticle specific toxicity when exposed to ZnO and CuO nanoparticles.

PubMed

Adam, Nathalie; Vergauwen, Lucia; Blust, Ronny; Knapen, Dries

2015-04-01

There is still a lot of contradiction on whether metal ions are solely responsible for the observed toxicity of ZnO and CuO nanoparticles to aquatic species. While most experiments have studied nanoparticle effects at organismal levels (e.g. mortality, reproduction), effects at lower levels of biological organization may clarify the role of metal ions, nanoparticles and nanoparticle aggregates. In this study, the effect of ZnO and CuO nanoparticles was tested at two lower levels: energy reserves and gene transcription and compared with zinc and copper salts. Daphnia magna was exposed during 96h to 10% immobilization concentrations of all chemicals, after which daphnids were sampled for determination of glycogen, lipid and protein concentration and for a differential gene transcription analysis using microarray. The dissolved, nanoparticle and aggregated fraction in the medium was characterized. The results showed that ZnO nanoparticles had largely dissolved directly after addition to the test medium. The CuO nanoparticles mostly formed aggregates, while only a small fraction dissolved. The exposure to zinc (both nano and metal salt) had no effect on the available energy reserves. However, in the copper exposure, the glycogen, lipid and protein concentration in the exposed daphnids was lower than in the unexposed ones. When comparing the nanoparticle (ZnO or CuO) exposed daphnids to the metal salt (zinc or copper salt) exposed daphnids, the microarray results showed no significantly differentially transcribed gene fragments. The results indicate that under the current exposure conditions the toxicity of ZnO and CuO nanoparticles to D. magna is solely caused by toxic metal ions. Copyright © 2015 Elsevier Inc. All rights reserved.

Cu{sub 2}ZnSnS{sub 4} nanoflakes prepared by one step microwave irradiation technique: Effect of Cu concentration

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

Kandare, S. P.; Dhole, S. D.; Bhoraskar, V. N.

Cu{sub 2}ZnSnS{sub 4} (CZTS) nanoflakes were synthesized in one step by microwave irradiation method. Controlling the secondary phases in Copper Zinc Tin Sulfide (CZTS) material is critical, but it is necessary to control secondary phases in order to achieve the high efficiency solar cells made from CZTS. In the recent years, CZTS has shown its growing importance in thin film photovoltaic application because of its favorable optical and electrical properties. In this work, a systematic study has been carried out by properly controlling the copper concentration to get the pure phase of CZTS. X-ray diffraction shows the CZTS kesterite structure.more » Optical band gap estimated from UV-Visible spectroscopy was around 1.37eV. Systematic Raman study reveals the suppression of Cu{sub 2}S peak with variation in copper concentration which otherwise was not clear from XRD and UV-visible data.« less

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

PubMed Central

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

2016-01-01

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

Neutropenia restores virulence to an attenuated Cu,Zn superoxide dismutase-deficient Haemophilus ducreyi strain in the swine model of chancroid.

PubMed

San Mateo, L R; Toffer, K L; Orndorff, P E; Kawula, T H

1999-10-01

Haemophilus ducreyi causes chancroid, a sexually transmitted cutaneous genital ulcer disease associated with increased heterosexual transmission of human immunodeficiency virus. H. ducreyi expresses a periplasmic copper-zinc superoxide dismutase (Cu, Zn SOD) that protects the bacterium from killing by exogenous superoxide in vitro. We hypothesized that the Cu,Zn SOD would protect H. ducreyi from immune cell killing, enhance survival, and affect ulcer development in vivo. In order to test this hypothesis and study the role of the Cu,Zn SOD in H. ducreyi pathogenesis, we compared a Cu,Zn SOD-deficient H. ducreyi strain to its isogenic wild-type parent with respect to survival and ulcer development in immunocompetent and immunosuppressed pigs. The Cu,Zn SOD-deficient strain was recovered from significantly fewer inoculated sites and in significantly lower numbers than the wild-type parent strain or a merodiploid (sodC+ sodC) strain after infection of immunocompetent pigs. In contrast, survival of the wild-type and Cu,Zn SOD-deficient strains was not significantly different in pigs that were rendered neutropenic by treatment with cyclophosphamide. Ulcer severity in pigs was not significantly different between sites inoculated with wild type and sites inoculated with Cu,Zn SOD-deficient H. ducreyi. Our data suggest that the periplasmic Cu,Zn SOD is an important virulence determinant in H. ducreyi, protecting the bacterium from host immune cell killing and contributing to survival and persistence in the host.

Neutropenia Restores Virulence to an Attenuated Cu,Zn Superoxide Dismutase-Deficient Haemophilus ducreyi Strain in the Swine Model of Chancroid

PubMed Central

San Mateo, Lani R.; Toffer, Kristen L.; Orndorff, Paul E.; Kawula, Thomas H.

1999-01-01

Haemophilus ducreyi causes chancroid, a sexually transmitted cutaneous genital ulcer disease associated with increased heterosexual transmission of human immunodeficiency virus. H. ducreyi expresses a periplasmic copper-zinc superoxide dismutase (Cu,Zn SOD) that protects the bacterium from killing by exogenous superoxide in vitro. We hypothesized that the Cu,Zn SOD would protect H. ducreyi from immune cell killing, enhance survival, and affect ulcer development in vivo. In order to test this hypothesis and study the role of the Cu,Zn SOD in H. ducreyi pathogenesis, we compared a Cu,Zn SOD-deficient H. ducreyi strain to its isogenic wild-type parent with respect to survival and ulcer development in immunocompetent and immunosuppressed pigs. The Cu,Zn SOD-deficient strain was recovered from significantly fewer inoculated sites and in significantly lower numbers than the wild-type parent strain or a merodiploid (sodC+ sodC) strain after infection of immunocompetent pigs. In contrast, survival of the wild-type and Cu,Zn SOD-deficient strains was not significantly different in pigs that were rendered neutropenic by treatment with cyclophosphamide. Ulcer severity in pigs was not significantly different between sites inoculated with wild type and sites inoculated with Cu,Zn SOD-deficient H. ducreyi. Our data suggest that the periplasmic Cu,Zn SOD is an important virulence determinant in H. ducreyi, protecting the bacterium from host immune cell killing and contributing to survival and persistence in the host. PMID:10496915

Chemical Synthesis of ZnS:Cu Nanosheets

NASA Astrophysics Data System (ADS)

Bodo, Bhaskarjyoti; Kalita, P. K.

2010-10-01

ZnS thin films are synthesized through chemical bath deposition (CBD) technique from aqueous solution of ZnSO4 and thiourea mixing in equal volume and equimolar ratio. A 1% CuSO4 solution is mixed with the ZnSO4 solution for doping before the final chemical reaction. SEM image shows the formation of mainly nanosheets, teeth and comb like structures. Absorption studies show red shift of enhanced band gap on Cu doping. Photoluminescence of ZnS:Cu reveals the enhancement of blue luminescence at 468 nm and low intensity green emission at 493 nm which is attributed to more Cu2+ lying in the interstices. XRD shows that the prepared ZnS nanophosphors possess cubic zinc blende structures.

A New Test of Copper and Zinc Abundances in Late-type Stars Using Ultraviolet Cu II and Zn II Lines

NASA Astrophysics Data System (ADS)

Roederer, Ian U.; Barklem, Paul S.

2018-04-01

We present new abundances derived from Cu I, Cu II, Zn I, and Zn II lines in six warm (5766 ≤ {T}eff} ≤ 6427 K), metal-poor (‑2.50 ≤ [Fe/H] ≤ ‑0.95) dwarf and subgiant (3.64 ≤ log g ≤ 4.44) stars. These abundances are derived from archival high-resolution ultraviolet spectra from the Space Telescope Imaging Spectrograph on board the Hubble Space Telescope and ground-based optical spectra from several observatories. Ionized Cu and Zn are the majority species, and abundances derived from Cu II and Zn II lines should be largely insensitive to departures from local thermodynamic equilibrium (LTE). We find good agreement between the [Zn/H] ratios derived separately from Zn I and Zn II lines, suggesting that departures from LTE are, at most, minimal (≲0.1 dex). We find that the [Cu/H] ratios derived from Cu II lines are 0.36 ± 0.06 dex larger than those derived from Cu I lines in the most metal-poor stars ([Fe/H] < ‑1.8), suggesting that LTE underestimates the Cu abundance derived from Cu I lines. The deviations decrease in more metal-rich stars. Our results validate previous theoretical non-LTE calculations for both Cu and Zn, supporting earlier conclusions that the enhancement of [Zn/Fe] in metal-poor stars is legitimate, and the deficiency of [Cu/Fe] in metal-poor stars may not be as large as previously thought. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained from the data archive at the Space Telescope Science Institute (STScI), which is operated by the Association of Universities for Research in Astronomy, Inc. (AURA) under NASA contract NAS 5-26555. This work is supported by NASA through grant number AR-15051 and makes use of data from programs GO-7348, GO-8197, GO-9804, GO-14161, and GO-14672. This research has also made use of the Keck Observatory Archive (KOA), which is operated by the W.M. Keck Observatory and the NASA Exoplanet Science Institute (NExScI), under contract with NASA. These data are associated

Surface characterization of ZnO/ZnMn2O4 and Cu/Mn3O4 powders obtained by thermal degradation of heterobimetallic complexes

NASA Astrophysics Data System (ADS)

Barrault, Joël; Makhankova, Valeriya G.; Khavryuchenko, Oleksiy V.; Kokozay, Vladimir N.; Ayrault, Philippe

2012-03-01

From the selective transformation of the heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes with 2,2'-bipyridyl by thermal degradation at relatively low (350 °C) temperature, it was possible to get either well defined spinel ZnMn2O4 over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn3O4) in a core-shell like structure. Morphology of the powder surface was examined by scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX). Surface composition was determined by X-ray photoelectron spectroscopy (XPS). Specific surface of the powders by nitrogen adsorption was found to be 33±0.2 and 9±0.06 m2 g-1 for Zn-Mn and Cu-Mn samples, respectively, which is comparable to those of commercial products.

Eradication of multi-drug resistant bacteria by a novel Zn-doped CuO nanocomposite.

PubMed

Malka, Eyal; Perelshtein, Ilana; Lipovsky, Anat; Shalom, Yakov; Naparstek, Livnat; Perkas, Nina; Patick, Tal; Lubart, Rachel; Nitzan, Yeshayahu; Banin, Ehud; Gedanken, Aharon

2013-12-09

Zinc-doped copper oxide nanoparticles are synthesized and simultaneously deposited on cotton fabric using ultrasound irradiation. The optimization of the processing conditions, the specific reagent ratio, and the precursor concentration results in the formation of uniform nanoparticles with an average size of ≈30 nm. The antibacterial activity of the Zn-doped CuO Cu₀.₈₈Zn₀.₁₂O in a colloidal suspension or deposited on the fabric is tested against Escherichia coli (Gram negative) and Staphylococcus aureus (Gram positive) bacteria. A substantial enhancement of 10,000 times in the antimicrobial activity of the Zn-CuO nanocomposite compared to the pure CuO and ZnO nanoparticles (NPs) is observed after 10 min exposure to the bacteria. Similar activities are observed against multidrug-resistant bacteria (MDR), (i.e., Methicillin-resistant S. aureus and MDR E. coli) further emphasizing the efficacy of this composite. Finally, the mechanism for this enhanced antibacterial activity is presented. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Accumulation and toxicity of CuO and ZnO nanoparticles through waterborne and dietary exposure of goldfish (Carassius auratus).

PubMed

Ates, Mehmet; Arslan, Zikri; Demir, Veysel; Daniels, James; Farah, Ibrahim O

2015-01-01

Dietary and waterborne exposure to copper oxide (CuO) and zinc oxide (ZnO) nanoparticles (NPs) was conducted using a simplified model of an aquatic food chain consisting of zooplankton (Artemia salina) and goldfish (Carassius auratus) to determine bioaccumulation, toxic effects, and particle transport through trophic levels. Artemia contaminated with NPs were used as food in dietary exposure. Fish were exposed to suspensions of the NPs in waterborne exposure. ICP-MS analysis showed that accumulation primarily occurred in the intestine, followed by the gills and liver. Dietary uptake was lower, but was found to be a potential pathway for transport of NPs to higher organisms. Waterborne exposure resulted in about a 10-fold higher accumulation in the intestine. The heart, brain, and muscle tissue had no significant Cu or Zn. However, concentrations in muscle increased with NP concentration, which was ascribed to bioaccumulation of Cu and Zn released from NPs. Free Cu concentration in the medium was always higher than that of Zn, indicating CuO NPs dissolved more readily. ZnO NPs were relatively benign, even in waterborne exposure (p ≥ 0.05). In contrast, CuO NPs were toxic. Malondialdehyde levels in the liver and gills increased substantially (p < 0.05). Despite lower Cu accumulation, the liver exhibited significant oxidative stress, which could be from chronic exposure to Cu ions. © 2014 Wiley Periodicals, Inc.

Coal-burning endemic fluorosis is associated with reduced activity in antioxidative enzymes and Cu/Zn-SOD gene expression.

PubMed

Wang, Qi; Cui, Kang-ping; Xu, Yuan-yuan; Gao, Yan-ling; Zhao, Jing; Li, Da-sheng; Li, Xiao-lei; Huang, Hou-jin

2014-02-01

To study the effect of fluorine on the oxidative stress in coal-burning fluorosis, we investigated the environmental characteristics of coal-burning endemic fluorosis combined with fluorine content surveillance in air, water, food, briquette, and clay binder samples from Bijie region, Guizhou Province, southwest of China. The activities of antioxidant enzymes including copper/zinc superoxide dismutase (Cu/Zn-SOD), catalase (CAT), glutathione peroxidase (GSH-Px), and level of lipid peroxidation such as malondialdehyde (MDA) were measured in serum samples obtained from subjects residing in the Bijie region. Expression of the Cu/Zn-SOD gene was assessed by quantitative reverse transcriptase PCR (qRT-PCR). Our results showed that people suffering from endemic fluorosis (the high and low exposure groups) had much higher MDA level. Their antioxidant enzyme activities and Cu/Zn-SOD gene expression levels were lower when compared to healthy people (the control group). Fluorosis can decrease the activities of antioxidant enzymes, which was associated with exposure level of fluorine. Down-regulation of Cu/Zn-SOD expression may play an important role in the aggravation of oxidative stress in endemic fluorosis.

Comparative toxicity of metal oxide nanoparticles (CuO, ZnO and TiO2) to developing zebrafish embryos

NASA Astrophysics Data System (ADS)

Vicario-Parés, Unai; Castañaga, Luis; Lacave, Jose Maria; Oron, Miriam; Reip, Paul; Berhanu, Deborah; Valsami-Jones, Eugenia; Cajaraville, Miren P.; Orbea, Amaia

2014-08-01

Increasing use of nanomaterials is resulting in their release into the environment, making necessary to determine the toxicity of these materials. With this aim, the effects of CuO, ZnO and TiO2 nanoparticles (NPs) on zebrafish development were assessed in comparison with the effects caused by the ionic forms (for copper and zinc), bulk counterparts and the stabilizer used for rutile TiO2 NPs. None of the NPs caused significant embryo mortality. CuO NPs were the most toxic affecting hatching and increasing malformation prevalence (≥1 mg Cu/L), followed by ZnO NPs that affected hatching at ≥5 mg Zn/L and stabilized TiO2 NPs that caused mortality and decreased hatching at 100 mg Ti/L. Exposure to the stabilizer alone provoked the same effect. Thus, toxicity of the TiO2 NP suspension can be linked to the surfactant. For all the endpoints, the greatest effects were exerted by the ionic forms, followed by the NPs and finally by the bulk compounds. By autometallography, metal-bearing deposits were observed in embryos exposed to CuO and ZnO NPs, being more abundant in the case of embryos exposed to CuO NPs. The largest and most abundant metal-bearing deposits were detected in embryos exposed to ionic copper. In conclusion, metal oxide NPs affected zebrafish development altering hatching and increasing the prevalence of malformations. Thus, the use and release of metal oxide NPs to the environment may pose a risk to aquatic organisms as a result of the toxicity caused by NPs themselves or by the additives used in their production.

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

DOE PAGES

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

2016-08-17

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

Complete transformation of ZnO and CuO nanoparticles in ...

EPA Pesticide Factsheets

Here, we present evidence on complete transformation of ZnO and CuO nanoparticles, which are among the most heavily studied metal oxide particles, during 24 h in vitro toxicological testing with human T-lymphocytes. Synchrotron radiation-based X-ray absorption near edge structure (XANES) spectroscopy results revealed that Zn speciation profiles of 30 nm and 80 nm ZnO nanoparticles, and ZnSO4- exposed cells were almost identical with the prevailing species being Zn-cysteine. This suggests that ZnO nanoparticles are rapidly transformed during a standard in vitro toxicological assay, and are sequestered intracellularly, analogously to soluble Zn. Complete transformation of ZnO in the test conditions was further supported by almost identical Zn spectra in medium to which ZnO nanoparticles or ZnSO4 was added. Likewise, Cu XANES spectra for CuO and CuSO4-exposed cells and cell culture media were similar. These results together with our observation on similar toxicological profiles of ZnO and soluble Zn, and CuO and soluble Cu, underline the importance of dissolution and subsequent transformation of ZnO and CuO nanoparticles during toxicological testing and provide evidence that the nano-specific effect of ZnO and CuO nanoparticulates is negligible in this system. We strongly suggest to account for this aspect when interpreting the toxicological results of ZnO and CuO nanoparticles. Although a number of studies have discussed the transformation of nanoparticles during

Do Cd, Cu, Ni, Pb, and Zn biomagnify in aquatic ecosystems?

PubMed

Cardwell, Rick D; Deforest, David K; Brix, Kevin V; Adams, William J

2013-01-01

In this review, we sought to assess from a study of the literature whether five in organic metals (viz., cadmium, copper, lead, nickel, and zinc) bio magnify in aquatic food webs. We also examined whether accumulated metals were toxic to consumers/predators and whether the essential metals (Cu and Zn and possibly Ni) behaved differently from non-essential ones (Cd and Pb). Biomagnification potential was indexed by the magnitude of single and multiple trophic transfers in food chains. In this analysis, we used three lines of evidence-laboratory empirical, biokinetic modeling, and field studies-to make assessments. Trophic transfer factors, calculatedfrom lab studies, field studies, and biokinetic modeling, were generally congruent.Results indicated that Cd, Cu, Pb, and Zn generally do not biomagnify in food chains consisting of primary producers, macro invertebrate consumers, and fish occupying TL 3 and higher. However, bio magnification of Zn (TTFs of 1-2) is possible for circumstances in which dietary Zn concentrations are below those required for metabolism. Cd, Cu, Ni, and Zn may biomagnify in specific marine food chains consisting of bivalves, herbivorous gastropods, and barnacles at TL2 and carnivorous gastropods at TL3. There was an inverse relationship between TTF and exposure concentration for Cd, Cu, Pb, and Zn, a finding that is consistent with previous reviews of bioconcentration factors and bioaccumulation factors for metals. Our analysis also failed to demonstrate a relationship between the magnitude of TTFsand dietary toxicity to consumer organisms. Consequently, we conclude that TTFs for the metals examined are not an inherently useful predictor of potential hazard(i.e., toxic potential) to aquatic organisms. This review identified several uncertainties or data gaps, such as the relatively limited data available for nickel, reliance upon highly structured food chains in laboratory studies compared to the unstructured food webs found in nature, and

Interfacial Phenomena in Al/Al, Al/Cu, and Cu/Cu Joints Soldered Using an Al-Zn Alloy with Ag or Cu Additions

NASA Astrophysics Data System (ADS)

Pstruś, Janusz; Gancarz, Tomasz

2014-05-01

The studies of soldered joints were carried out in systems: Al/solder/Al, Al/solder/Cu, Cu/solder/Cu, where the solder was (Al-Zn)EUT, (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Ag and (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Cu addition. Brazing was performed at 500 °C for 3 min. The EDS analysis indicated that the composition of the layers starting from the Cu pad was CuZn, Cu5Zn8, and CuZn4, respectively. Wetting tests were performed at 500 °C for 3, 8, 15, and 30 min, respectively. Thickness of the layers and their kinetics of growth were measured based on the SEM micrographs. The formation of interlayers was not observed from the side of Al pads. On the contrary, dissolution of the Al substrate and migration of Al-rich particles into the bulk of the solder were observed.

Assessment of Ni, Cu, Zn and Pb levels in beach and dune sands from Havana resorts, Cuba.

PubMed

Díaz Rizo, Oscar; Buzón González, Fran; Arado López, Juana O

2015-11-15

Concentrations of nickel (Ni), copper (Cu), zinc (Zn) and lead (Pb) in beach and dune sands from thirteen Havana (Cuba) resorts were estimated by X-ray fluorescence analysis. Determined mean metal contents (in mg·kg(-1)) in beach sand samples were 28±12 for Ni, 35±12 for Cu, 31±11 for Zn and 6.0±1.8 for Pb, while for dune sands were 30±15, 38±22, 37±15 and 6.8±2.9, respectively. Metal-to-iron normalization shows moderately severe and severe enrichment by Cu. The comparison with sediment quality guidelines shows that dune sands from various resorts must be considered as heavily polluted by Cu and Ni. Almost in every resort, the Ni and Cu contents exceed their corresponding TEL values and, in some resorts, the Ni PEL value. The comparison with a Havana topsoil study indicates the possible Ni and Cu natural origin. Copyright © 2015 Elsevier Ltd. All rights reserved.

Glassy behavior of diluted Cu-Zn ferrites

NASA Astrophysics Data System (ADS)

Akhter, Shahida; Hakim, M. A.; Hoque, S. M.; Mathieu, R.; Nordblad, P.

2018-04-01

The magnetic behavior of Zn substituted Cu-Zn spinel ferrites having chemical formula Cu1-xZnxFe2O4 (x = 0.7, 0.8, 0.9 and 1.0) has been studied by SQUID magnetometry, by means of magnetic hysteresis, field-cooled (FC) and zero-field-cooled (ZFC) magnetization, memory effect and low field ac susceptibility measurements. These measurements suggest that the ferrimagnetic phase of the x ≤ 0.8 samples is gradually turned into a spin glass (x ≥ 0.9). The compound with x = 0.9 exhibits the typical dynamical behavior of spin glasses, with indication of aging, rejuvenation and memory effects. The evolution of the magnetic properties of Cu-Zn spinel ferrites with substitution of Zn for Cu is discussed.

Real-time observation of Cu2ZnSn(S,Se)4 solar cell absorber layer formation from nanoparticle precursors.

PubMed

Mainz, Roland; Walker, Bryce C; Schmidt, Sebastian S; Zander, Ole; Weber, Alfons; Rodriguez-Alvarez, Humberto; Just, Justus; Klaus, Manuela; Agrawal, Rakesh; Unold, Thomas

2013-11-07

The selenization of Cu-Zn-Sn-S nanocrystals is a promising route for the fabrication of low-cost thin film solar cells. However, the reaction pathway of this process is not completely understood. Here, the evolution of phase formation, grain size, and elemental distributions is investigated during the selenization of Cu-Zn-Sn-S nanoparticle precursor thin films by synchrotron-based in situ energy-dispersive X-ray diffraction and fluorescence analysis as well as by ex situ electron microscopy. The precursor films are heated in a closed volume inside a vacuum chamber in the presence of selenium vapor while diffraction and fluorescence signals are recorded. The presented results reveal that during the selenization the cations diffuse to the surface to form large grains on top of the nanoparticle layer and the selenization of the film takes place through two simultaneous reactions: (1) a direct and fast formation of large grained selenides, starting with copper selenide which is subsequently transformed into Cu2ZnSnSe4; and (2) a slower selenization of the remaining nanoparticles. As a consequence of the initial formation of copper selenides at the surface, the subsequent formation of CZTSe starts under Cu-rich conditions despite an overall Cu-poor composition of the film. The implications of this process path for the film quality are discussed. Additionally, the proposed growth model provides an explanation for the previously observed accumulation of carbon from the nanoparticle precursor beneath the large grained layer.

Zinc, copper, and lead in mid-ocean ridge basalts and the source rock control on Zn/Pb in ocean-ridge hydrothermal deposits

USGS Publications Warehouse

Doe, B.R.

1994-01-01

The contents of Zn, Cu, and Pb in mid-ocean ridge basalts (MORB) and the MORB source-rock control on Zn/Pb in ocean-ridge hydrothermal deposits are examined. The values of Zn, Cu, and Pb for submarine mid-ocean ridge basalts (MORB) are, respectively (in ppm): average MORB-75, 75, and 0.7; West Valley, Juan de Fuca Ridge (JFR)-87, 64, and 0.5; southern JFR-120 and 0.5; and 21??N, East Pacific Rise (EPR)-73, 78, and 0.5. Values of Zn/Pb range from about 100-240 and Cu/ Pb from 100-156. In this study, Zn is found to correlate positively with TiO2 + FeO (mean square of weighted deviates, MSWD, of 1.6 for JFR basalt), and inversely with Mg number (MSWD of 3.5). Therefore, contrary to statements in the literature that Zn should be compatible in MORB, Zn is a mildly incompatible element and must be enriched in the glass phase relative to olivine as Zn does not fit into the other major phenocryst phase, plagioclase. In the source of MORB, Zn likely is most enriched in oxides: spinel, magnetite, and titanomagnetite. Copper generally does not correlate well with other elements in most MORB data examined. When differentiation is dominated by olivine, Cu has a tendency to behave incompatibly (e.g., at Mg numbers > 70), but, overall, Cu shows some tendency towards being a compatible element, particularly along the Mid-Atlantic Ridge, a behavior presumably due to separation of sulfides in which Cu (but not Zn) is markedly enriched. Copper thus may be in dispersed sulfides in the source of MORB. Ocean ridges provide important data on source-rock controls for sulfide deposits because, in sediment-starved ridges, much is known about the possible source rocks and mineralization is presently occurring. In contrast to Zn/Pb ~5 in continental hot Cl-rich brines, Zn/Pb in the hottest sediment-starved ridge black smoker hydrothermal fluids at 21 ??N, EPR is about 110, similar to local MORB (145), but Cu/Pb is closer to 30, possibly due to subsurface deposition of Cu. At the JFR, the best

Changes in urinary Cu, Zn, and Se levels in cancer patients after treatment with Sha Shen Mai Men Dong Tang

PubMed Central

Lai, Tung-Yuan; Kuo, Hsien-Wen

2015-01-01

Sha Shen Mai Men Dong Tang (SMD-2; 沙參麥冬湯 shā shēn mài dōng tāng) is a Chinese medicinal herb (CMH; 中草藥 zhōng cǎo yào) used to treat symptoms associated with cancer therapy. The objective of this study was to assess the effect of SMD-2 on the levels of urinary copper (Cu), zinc (Zn), and selenium (Se) in lung cancer patients and head and neck cancer patients receiving chemoradiotherapy. Forty-two head and neck cancer patients and 10 lung cancer patients participated in our clinical trial. Each patient received chemoradiotherapy for 4 weeks. In addition, each patient was treated with SMD-2 for 8 weeks, including 2 weeks prior to and after the chemoradiotherapy treatment. Comparison of urinary Cu, Zn, and Se levels and the ratios of Zn to Cu and Se to Cu at three time points in the two types of cancer were assessed using the generalized estimating equations (GEEs). After the patients received chemoradiotherapy for 4 weeks, SMD-2 treatment was found to be associated with a significant decrease in urinary Cu levels, whereas urinary Zn and Se levels increased significantly. In addition, the ratios of Zn to Cu and Se to Cu in the urine samples of these patients also increased significantly. Both the urinary Zn levels and the ratio of Zn to Cu in head and neck cancer patients were significantly higher than in lung cancer patients. Urinary Zn and Se levels and the ratios of Zn to Cu and Se to Cu, but not urinary Cu levels, increased significantly during and after treatment when assessed using the GEE model. The SMD-2 treatments significantly increased Zn and Se levels in the urine of head and neck cancer patients. Increased Zn and Se levels in urine strengthened immune system. PMID:27114935

Cu-Zn isotope constraints on the provenance of air pollution in Central Europe: Using soluble and insoluble particles in snow and rime.

PubMed

Novak, Martin; Sipkova, Adela; Chrastny, Vladislav; Stepanova, Marketa; Voldrichova, Petra; Veselovsky, Frantisek; Prechova, Eva; Blaha, Vladimir; Curik, Jan; Farkas, Juraj; Erbanova, Lucie; Bohdalkova, Leona; Pasava, Jan; Mikova, Jitka; Komarek, Arnost; Krachler, Michael

2016-11-01

Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ 65 Cu and δ 66 Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ 65 Cu and δ 66 Zn values in snow and rime, extracted by diluted HNO 3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ 65 Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ 65 Cu value of pollution sources (-1.17‰). The variability in δ 65 Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ 66 Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ 66 Zn value of pollution sources (-0.23‰). The variability in δ 66 Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe. Copyright © 2016 Elsevier Ltd. All rights reserved.

Study on room temperature gas-sensing performance of CuO film-decorated ordered porous ZnO composite by In2O3 sensitization

PubMed Central

Li, Tian-tian; Bao, Na; Geng, Ai-fang; Yang, Ying; Dong, Xiang-ting

2018-01-01

For the first time, ordered mesoporous ZnO nanoparticles have been synthesized by a template method. The electroplating after chemical plating method was creatively used to form copper film on the surface of the prepared ZnO, and then a CuO film-decorated ordered porous ZnO composite (CuO/ZnO) was obtained by a high-temperature oxidation method. In2O3 was loaded into the prepared CuO film–ZnO by an ultrasonic-assisted method to sensitize the room temperature gas-sensing performance of the prepared CuO/ZnO materials. The doped In2O3 could effectively improve the gas-sensing properties of the prepared materials to nitrogen oxides (NOx) at room temperature. The 1% In2O3 doped CuO/ZnO sample (1 wt% In2O3–CuO/ZnO) showed the best gas-sensing properties whose response to 100 ppm NOx reached 82%, and the detectable minimum concentration reached 1 ppm at room temperature. The prepared materials had a good selectivity, better response, very low detection limit, and high sensitivity to NOx gas at room temperature, which would have a great development space in the gas sensor field and a great research value. PMID:29515887

Study on room temperature gas-sensing performance of CuO film-decorated ordered porous ZnO composite by In2O3 sensitization

NASA Astrophysics Data System (ADS)

Li, Tian-tian; Bao, Na; Geng, Ai-fang; Yu, Hui; Yang, Ying; Dong, Xiang-ting

2018-02-01

For the first time, ordered mesoporous ZnO nanoparticles have been synthesized by a template method. The electroplating after chemical plating method was creatively used to form copper film on the surface of the prepared ZnO, and then a CuO film-decorated ordered porous ZnO composite (CuO/ZnO) was obtained by a high-temperature oxidation method. In2O3 was loaded into the prepared CuO film-ZnO by an ultrasonic-assisted method to sensitize the room temperature gas-sensing performance of the prepared CuO/ZnO materials. The doped In2O3 could effectively improve the gas-sensing properties of the prepared materials to nitrogen oxides (NOx) at room temperature. The 1% In2O3 doped CuO/ZnO sample (1 wt% In2O3-CuO/ZnO) showed the best gas-sensing properties whose response to 100 ppm NOx reached 82%, and the detectable minimum concentration reached 1 ppm at room temperature. The prepared materials had a good selectivity, better response, very low detection limit, and high sensitivity to NOx gas at room temperature, which would have a great development space in the gas sensor field and a great research value.

Optimization of Cu-Zn Massive Sulphide Flotation by Selective Reagents

NASA Astrophysics Data System (ADS)

Soltani, F.; Koleini, S. M. J.; Abdollahy, M.

2014-10-01

Selective floatation of base metal sulphide minerals can be achieved by using selective reagents. Sequential floatation of chalcopyrite-sphalerite from Taknar (Iran) massive sulphide ore with 3.5 % Zn and 1.26 % Cu was studied. D-optimal design of response surface methodology was used. Four mixed collector types (Aer238 + SIPX, Aero3477 + SIPX, TC1000 + SIPX and X231 + SIPX), two depressant systems (CuCN-ZnSO4 and dextrin-ZnSO4), pH and ZnSO4 dosage were considered as operational factors in the first stage of flotation. Different conditions of pH, CuSO4 dosage and SIPX dosage were studied for sphalerite flotation from first stage tailings. Aero238 + SIPX induced better selectivity for chalcopyrite against pyrite and sphalerite. Dextrin-ZnSO4 was as effective as CuCN-ZnSO4 in sphalerite-pyrite depression. Under optimum conditions, Cu recovery, Zn recovery and pyrite content in Cu concentrate were 88.99, 33.49 and 1.34 % by using Aero238 + SIPX as mixed collector, CuCN-ZnSO4 as depressant system, at ZnSO4 dosage of 200 g/t and pH 10.54. When CuCN was used at the first stage, CuSO4 consumption increased and Zn recovery decreased during the second stage. Maximum Zn recovery was 72.19 % by using 343.66 g/t of CuSO4, 22.22 g/t of SIPX and pH 9.99 at the second stage.

Crystal structure of bovine Cu,Zn superoxide dismutase at 3 A resolution: chain tracing and metal ligands.

PubMed Central

Richardson, J; Thomas, K A; Rubin, B H; Richardson, D C

1975-01-01

An electron density map at 3 angstrom resolution has been calculated for Cu2+, Zn2+ superoxide dismutase from bovine erythrocytes, and the course of the main chain has been traced. The dominant structural feature is an 8-stranded barrel of antiparallel beta-pleated sheet. There is one very short helical section and two long loops of non-repetitive structure. The Cu and Zn are bound between the loops and one side of the beta barrel and are about 6 Angstrom apart, with a common histidine ligand. The Cu has four histidine ligands in a somewhat distorted square plane, and the Zn has three histidines and an aspartate in approximately tetrahedral arrangement. The two coppers of a dimer are about 34 Angstrom apart. The two subunits have essentially the same conformation and have an extensive contact area that mainly involves hydrophobic side chain interactions. The overall folding pattern of the polypeptide chain is very similar to that of an immunoglobulin domain. Images PMID:1055410

CZTSe solar cells prepared by electrodeposition of Cu/Sn/Zn stack layer followed by selenization at low Se pressure

PubMed Central

2014-01-01

Cu2ZnSnSe4 (CZTSe) thin films are prepared by the electrodeposition of stack copper/tin/zinc (Cu/Sn/Zn) precursors, followed by selenization with a tin source at a substrate temperature of 530°C. Three selenization processes were performed herein to study the effects of the source of tin on the quality of CZTSe thin films that are formed at low Se pressure. Much elemental Sn is lost from CZTSe thin films during selenization without a source of tin. The loss of Sn from CZTSe thin films in selenization was suppressed herein using a tin source at 400°C (A2) or 530°C (A3). A copper-poor and zinc-rich CZTSe absorber layer with Cu/Sn, Zn/Sn, Cu/(Zn + Sn), and Zn/(Cu + Zn + Sn) with metallic element ratios of 1.86, 1.24, 0.83, and 0.3, respectively, was obtained in a selenization with a tin source at 530°C. The crystallized CZTSe thin film exhibited an increasingly (112)-preferred orientation at higher tin selenide (SnSe x ) partial pressure. The lack of any obvious Mo-Se phase-related diffraction peaks in the X-ray diffraction (XRD) diffraction patterns may have arisen from the low Se pressure in the selenization processes. The scanning electron microscope (SEM) images reveal a compact surface morphology and a moderate grain size. CZTSe solar cells with an efficiency of 4.81% were produced by the low-cost fabrication process that is elucidated herein. PMID:25593559

Accurate measurements of the 63Cu(d,p)64Cu and natCu(d,x)65Zn cross-sections in the 2.77-5.62 MeV energy range

NASA Astrophysics Data System (ADS)

Weissman, L.; Kreisel, A.; Hirsh, T.; Aviv, O.; Berkovits, D.; Girshevitz, O.; Eisen, Y.

2015-01-01

The cross sections of 63Cu(d,p)64Cu and natCu(d,x)65Zn were determined for deuteron beam energy range of 2.77-5.62 MeV at the SARAF Phase I variable energy LINAC. Thin copper foils were irradiated by a deuteron beam followed up by measurement of the produced activation at the Soreq NRC low-background γ-counting system. The results are consistent with data in the literature, but are of better accuracy. The data are important for assessment of the activation of components of Radio Frequency Quadrupole injectors and Medium Energy Beam Transport beam dumps in modern deuteron LINACs.

The role of interparticle heterogeneities in the selenization pathway of Cu-Zn-Sn-S nanoparticle thin films: A real-time study

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

Carter, Nathaniel J.; Mainz, Roland; Walker, Bryce C.

2015-06-10

Real-time energy dispersive x-ray diffraction (EDXRD) analysis has been utilized to observe the selenization of Cu-Zn-Sn-S nanoparticle films coated from three nanoparticle populations: Cu- and Sn-rich particles roughly 5 nm in size, Zn-rich nanoparticles ranging from 10 to 20 nm in diameter, and a mixture of both types of nanoparticles (roughly 1:1 by mass), which corresponds to a synthesis recipe yielding CZTSSe solar cells with reported total-area efficiencies as high as 7.9%. The EDXRD studies presented herein show that the formation of copper selenide intermediates during the selenization of mixed-particle films can be primarily attributed to the small, Cu- andmore » Sn-rich particles. Moreover, the formation of these copper selenide phases represents the first stage of the CZTSSe grain growth mechanism. The large, Zn-rich particles subsequently contribute their composition to form micrometer-sized CZTSSe grains. In conclusion, these findings enable further development of a previously proposed selenization pathway to account for the roles of interparticle heterogeneities, which in turn provides a valuable guide for future optimization of processes to synthesize high quality CZTSSe absorber layers.« less

Cu,Zn superoxide dismutase structure from a microbial pathogen establishes a class with a conserved dimer interface.

PubMed

Forest, K T; Langford, P R; Kroll, J S; Getzoff, E D

2000-02-11

Macrophages and neutrophils protect animals from microbial infection in part by issuing a burst of toxic superoxide radicals when challenged. To counteract this onslaught, many Gram-negative bacterial pathogens possess periplasmic Cu,Zn superoxide dismutases (SODs), which act on superoxide to yield molecular oxygen and hydrogen peroxide. We have solved the X-ray crystal structure of the Cu,Zn SOD from Actinobacillus pleuropneumoniae, a major porcine pathogen, by molecular replacement at 1.9 A resolution. The structure reveals that the dimeric bacterial enzymes form a structurally homologous class defined by a water-mediated dimer interface, and share with all Cu,Zn SODs the Greek-key beta-barrel subunit fold with copper and zinc ions located at the base of a deep loop-enclosed active-site channel. Our structure-based sequence alignment of the bacterial enzymes explains the monomeric nature of at least two of these, and suggests that there may be at least one additional structural class for the bacterial SODs. Two metal-mediated crystal contacts yielded our C222(1) crystals, and the geometry of these sites could be engineered into proteins recalcitrant to crystallization in their native form. This work highlights structural differences between eukaryotic and prokaryotic Cu,Zn SODs, as well as similarities and differences among prokaryotic SODs, and lays the groundwork for development of antimicrobial drugs that specifically target periplasmic Cu,Zn SODs of bacterial pathogens. Copyright 12000 Academic Press.

High-speed electrodeposition of copper-tin-zinc stacks from liquid metal salts for Cu2ZnSnSe4 solar cells.

PubMed

Steichen, Marc; Malaquias, João C; Arasimowicz, Monika; Djemour, Rabie; Brooks, Neil R; Van Meervelt, Luc; Fransaer, Jan; Binnemans, Koen; Dale, Phillip J

2017-01-16

Cu 2 ZnSnSe 4 -based solar cells with 5.5% power conversion efficiency were fabricated from Cu/Sn/Zn stacks electrodeposited from liquid metal salts. These electrolytes allow metal deposition rates one order of magnitude higher than those of other deposition methods.

Renierite, Cu10ZnGe2Fe4S16-Cu11GeAsFe4S16: a coupled solid solution series.

USGS Publications Warehouse

Bernstein, L.R.

1986-01-01

The composition of renierite is found to be Cu10(Zn1-xCux)Ge2-xAsxFe4S16 (0 = or < x = or < 1), with continuous solid solution between the zincian and arsenian end-members, Cu10ZnGe2Fe4S16 and Cu11GeAsFe4S16, through the coupled substitution Zn(II) + Ge(IV) = Cu(I) + As(V). This is the first reported example of extensive coupled solid solution in a sulphide mineral. Arsenian renierite, not previously characterized, is similar to zincian renierite in polished section, with a slightly redder colour and lower anisotropy. It is reddish orange with relief very similar to that of bornite, though it is harder (VHN25 = 286) and does not tarnish in air. It is slightly bireflective, with colours varying from orange-yellow to reddish orange in nearly crossed polarizers. The strongest powder XRD lines are: 3.042(100), 1.861(29), 1.869(16), 1.594(11) and 1.017(10) A; D(calc.) 4.50 g/cm3. Specimens have been found at the Ruby Creek copper deposit, Alaska, where zincian renierite also occurs, and at the Inexco no. 1 mine, Jamestown, Colorado.-J.A.Z.

Inflammation protects copper deficient rats from carbon tetrachloride toxicity

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

Yang, F.L.; Joseph, E.; DiSilvestro, R.A.

1991-03-11

Copper deficient rats show low resistance to CCl{sub 4}, possibly due to low liver Cu-Zn superoxide dismutase (SOD) activities. If Cu-Zn SOD is involved, deficiency effects should be aggravated by inflammation which further lowers Cu-Zn SOD activities in deficient rats. On the contrary, inflammation from 0.1 ml turpentine (im, lef) protected these rats from CCl{sub 4} damage assessed by serum activities of 2 liver enzymes. CCl{sub 4} was given ip at 200 {mu}l/kg, 48 h after turpentine, 24 h before sacrifice. Rats were fed low copper for 40 days before CCl{sub 4} challenge. Inflammation also protected rats fed adequate coppermore » from injury, though injury in noninflamed rats was less than with noninflamed deficients. Protection could result from the large increase observed in liver metallothionein, an induction not restricted by copper deficiency. Alternatively, inflammation may block P-450 activation of CCl{sub 4}. Both explanations are currently under investigation, as is the role, if any, of Cu-Zn SOD in resisting CCl{sub 4} injury.« less

Corrosion and runoff rates of Cu and three Cu-alloys in marine environments with increasing chloride deposition rate.

PubMed

Odnevall Wallinder, Inger; Zhang, Xian; Goidanich, Sara; Le Bozec, Nathalie; Herting, Gunilla; Leygraf, Christofer

2014-02-15

Bare copper sheet and three commercial Cu-based alloys, Cu15Zn, Cu4Sn and Cu5Al5Zn, have been exposed to four test sites in Brest, France, with strongly varying chloride deposition rates. The corrosion rates of all four materials decrease continuously with distance from the coast, i.e. with decreasing chloride load, and in the following order: Cu4Sn>Cu sheet>Cu15Zn>Cu5Al5Zn. The patina on all materials was composed of two main layers, Cu2O as the inner layer and Cu2(OH)3Cl as the outer layer, and with a discontinuous presence of CuCl in between. Additional minor patina constituents are SnO2 (Cu4Sn), Zn5(OH)6(CO3)2 (Cu15Zn and Cu5Al5Zn) and Zn6Al2(OH)16CO3·4H2O/Zn2Al(OH)6Cl·2H2O/Zn5Cl2(OH)8·H2O and Al2O3 (Cu5Al5Zn). The observed Zn- and Zn/Al-containing corrosion products might be important factors for the lower sensitivity of Cu15Zn and Cu5Al5Zn against chloride-induced atmospheric corrosion compared with Cu sheet and Cu4Sn. Decreasing corrosion rates with exposure time were observed for all materials and chloride loads and attributed to an improved adherence with time of the outer patina to the underlying inner oxide. Flaking of the outer patina layer was mainly observed on Cu4Sn and Cu sheet and associated with the gradual transformation of CuCl to Cu2(OH)3Cl of larger volume. After three years only Cu5Al5Zn remains lustrous because of a patina compared with the other materials that appeared brownish-reddish. Significantly lower release rates of metals compared with corresponding corrosion rates were observed for all materials. Very similar release rates of copper from all four materials were observed during the fifth year of marine exposure due to an outer surface patina that with time revealed similar constituents and solubility properties. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Elastocaloric effect in CuAlZn and CuAlMn shape memory alloys under compression

PubMed Central

Qian, Suxin; Wang, Yi; Pillsbury, Thomas E.; Hada, Yoshiharu; Yamaguchi, Yuki; Fujimoto, Kenjiro; Hwang, Yunho; Radermacher, Reinhard; Cui, Jun; Yuki, Yoji; Toyotake, Koutaro; Takeuchi, Ichiro

2016-01-01

This paper reports the elastocaloric effect of two Cu-based shape memory alloys: Cu68Al16Zn16 (CuAlZn) and Cu73Al15Mn12 (CuAlMn), under compression at ambient temperature. The compression tests were conducted at two different rates to approach isothermal and adiabatic conditions. Upon unloading at a strain rate of 0.1 s−1 (adiabatic condition) from 4% strain, the highest adiabatic temperature changes (ΔTad) of 4.0 K for CuAlZn and 3.9 K for CuAlMn were obtained. The maximum stress and hysteresis at each strain were compared. The stress at the maximum recoverable strain of 4.0% for CuAlMn was 120 MPa, which is 70% smaller than that of CuAlZn. A smaller hysteresis for the CuAlMn alloy was also obtained, about 70% less compared with the CuAlZn alloy. The latent heat, determined by differential scanning calorimetry, was 4.3 J g−1 for the CuAlZn alloy and 5.0 J g−1 for the CuAlMn alloy. Potential coefficients of performance (COPmat) for these two alloys were calculated based on their physical properties of measured latent heat and hysteresis, and a COPmat of approximately 13.3 for CuAlMn was obtained. This article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’. PMID:27402936

Interfacial engineering of CuO nanorod/ZnO nanowire hybrid nanostructure photoanode in dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Kilic, Bayram; Turkdogan, Sunay; Astam, Aykut; Baran, Sümeyra Seniha; Asgin, Mansur; Gur, Emre; Kocak, Yusuf

2018-01-01

Developing efficient and cost-effective photoanode plays a vital role determining the photocurrent and photovoltage in dye-sensitized solar cells (DSSCs). Here, we demonstrate DSSCs that achieve relatively high power conversion efficiencies (PCEs) by using one-dimensional (1D) zinc oxide (ZnO) nanowires and copper (II) oxide (CuO) nanorods hybrid nanostructures. CuO nanorod-based thin films were prepared by hydrothermal method and used as a blocking layer on top of the ZnO nanowires' layer. The use of 1D ZnO nanowire/CuO nanorod hybrid nanostructures led to an exceptionally high photovoltaic performance of DSSCs with a remarkably high open-circuit voltage (0.764 V), short current density (14.76 mA/cm2 under AM1.5G conditions), and relatively high solar to power conversion efficiency (6.18%) . The enhancement of the solar to power conversion efficiency can be explained in terms of the lag effect of the interfacial recombination dynamics of CuO nanorod-blocking layer on ZnO nanowires. This work shows more economically feasible method to bring down the cost of the nano-hybrid cells and promises for the growth of other important materials to further enhance the solar to power conversion efficiency.

Room temperature ferromagnetism in Cu doped ZnO

NASA Astrophysics Data System (ADS)

Ali, Nasir; Singh, Budhi; Khan, Zaheer Ahmed; Ghosh, Subhasis

2018-05-01

We report the room temperature ferromagnetism in 2% Cu doped ZnO films grown by RF magnetron sputtering in different argon and oxygen partial pressure. X-ray photoelectron spectroscopy was used to ascertain the oxidation states of Cu in ZnO. The presence of defects within Cu-doped ZnO films can be revealed by electron paramagnetic resonance. It has been observed that saturated magnetic moment increase as we increase the zinc vacancies during deposition.

In situ release rates of Cu and Zn from commercial antifouling paints at different salinities.

PubMed

Lagerström, Maria; Lindgren, J Fredrik; Holmqvist, Albin; Dahlström, Mia; Ytreberg, Erik

2018-02-01

Antifouling paints are environmentally risk assessed based on their biocidal release rates to the water phase. In situ release rates of copper (Cu) and zinc (Zn) were derived for five commercial paints in two recreational marinas with different salinities (5 and 14 PSU) using an X-Ray Fluorescence spectrometer (XRF). Salinity was found to significantly affect the Cu release, with twice the amount of Cu released at the higher salinity, while its influence on the Zn release was paint-specific. Site-specific release rates for water bodies with salinity gradients, e.g. the Baltic Sea, are therefore necessary for more realistic risk assessments of antifouling paints. Furthermore, the in situ release rates were up to 8 times higher than those generated using standardized laboratory or calculation methods. The environmental risk assessment repeated with the field release rates concludes that it is questionable whether the studied products should be allowed on the Swedish market. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Mechanical, structural and thermal properties of Ag-Cu and ZnO reinforced polylactide nanocomposite films.

PubMed

Ahmed, Jasim; Arfat, Yasir Ali; Castro-Aguirre, Edgar; Auras, Rafael

2016-05-01

Plasticized polylactic acid (PLA) based nanocomposite films were prepared by incorporating polyethylene glycol (PEG) and two selected nanoparticles (NPs) [silver-copper (Ag-Cu) alloy (<100 nm) and zinc oxide (ZnO) (<50 and <100 nm)] through solvent casting method. Incorporation of Ag-Cu alloy into the PLA/PEG matrix increased the glass transition temperature (Tg) significantly. The crystallinity of the nanocomposites (NCs) was significantly influenced by NP incorporation as evidenced from differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis. The PLA nanocomposite reinforced with NPs exhibited much higher tensile strength than that of PLA/PEG blend. Melt rheology of NCs exhibited a shear-thinning behavior. The mechanical property drastically reduced with a loading of NPs, which is associated with degradation of PLA. SEM micrographs exhibited that both Ag-Cu alloy and ZnO NPs were dispersed well in the PLA film matrix. Copyright © 2016 Elsevier B.V. All rights reserved.

Copper-Zinc Superoxide Dismutase: A Unique Biological "Ligand" for Bioinorganic Studies.

ERIC Educational Resources Information Center

Valentine, Joan Selverstone; de Freitas, Duarte Mota

1985-01-01

Discusses superoxide dismutase (SOD) research and the properties of copper, zinc (Cu, Zn)-SOD. Emphasizes the controversy concerning the role of Cu,Zn-SOD and other SOD enzymes as protective agents in reactions involving dioxygen metabolism, and the properties of Cu, Zn-SOD that make it an interesting biological ligand for physical studies of…

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

PubMed

Kattel, Shyam; Ramírez, Pedro J; Chen, Jingguang G; Rodriguez, José A; Liu, Ping

2017-09-01

In their Comment on the our recent Report, Nakamura et al argue that our x-ray photoelectron spectroscopy (XPS) analysis was affected by the presence of formate species on the catalyst surface. This argument is not valid because the reactant gases were evacuated at temperatures from 525 to 575 kelvin, conditions under which formate is not stable on the catalyst surface. An analysis of the XPS results obtained after exposing zinc oxide/copper (111) [ZnO/Cu(111)] surfaces to hydrogen (H 2 ) and mixtures of carbon dioxide (CO 2 )/H 2 show an absence of carbon (C) 1s signal, no asymmetries in the oxygen (O) 1s peak, and a Zn:O intensity close to 1:1. Thus, the most active phase of these catalysts contained a ZnO-Cu interface. Copyright © 2017, American Association for the Advancement of Science.

Preparation of Cu2ZnSnS4 nano-crystalline powder by mechano-chemical method

NASA Astrophysics Data System (ADS)

Alirezazadeh, Farzaneh; Sheibani, Saeed; Rashchi, Fereshteh

2018-01-01

Copper zinc tin sulfide (Cu2ZnSnS4, CZTS) is one of the most promising ceramic materials as an absorber layer in solar cells due to its suitable band gap, high absorption coefficient and non-toxic and environmental friendly constituent elements. In this work, nano-crystalline CZTS powder was synthesized by mechanical milling. Elemental powders of Cu, Zn, Sn and were mixed in atomic ratio of 2:1:1:4 according to the stoichiometry of Cu2ZnSnS4 and then milled in a planetary high energy ball mill under argon atmosphere. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffusion reflectance spectroscopy (DRS). XRD results confirm the formation of single-phase CZTS with kesterite structure after 20 h of milling. Also, the mean crystallite size was about 35 nm. SEM results show that after 20 h of milling, the product has a relatively uniform particle size distribution. Optical properties of the product indicate that the band gap of prepared CZTS is 1.6 eV which is near to the optimum value for photovoltaic solar cells showing as a light absorber material in solar energy applications.

ZnCuInS/ZnSe/ZnS quantum dot-based downconversion light-emitting diodes and their thermal effect

DOE PAGES

Liu, Wenyan; Zhang, Yu; Wang, Dan; ...

2015-08-13

The quantum dot-based light-emitting diodes (QD-LEDs) were fabricated using blue GaN chips and red-, yellow-, and green-emitting ZnCuInS/ZnSe/ZnS QDs. The power efficiencies were measured as 14.0 lm/W for red, 47.1 lm/W for yellow, and 62.4 lm/W for green LEDs at 2.6 V. The temperature effect of ZnCuInS/ZnSe/ZnS QDs on these LEDs was investigated using CIE chromaticity coordinates, spectral wavelength, full width at half-maximum (FWHM) and power efficiencies (PE). The thermal quenching induced by the increased surface temperature of the device was confirmed to be one of the important factors to decrease power efficiencies while the CIE chromaticity coordinates changed littlemore » due to the low emission temperature coefficients of 0.022, 0.050 and 0.068 nm/°C for red-, yellow- and green-emitting ZnCuInS/ZnSe/ZnS QDs. Lastly this indicates that ZnCuInS/ZnSe/ZnS QDs are more suitable for down-conversion LEDs compared to CdSe QDs.« less

Structure flexibility of the Cu2ZnSnS4 absorber in low-cost photovoltaic cells: from the stoichiometric to the copper-poor compounds.

PubMed

Choubrac, L; Lafond, A; Guillot-Deudon, C; Moëlo, Y; Jobic, S

2012-03-19

Here we present for the very first time a single-crystal investigation of the Cu-poor Zn-rich derivative of Cu(2)ZnSnS(4). Nowadays, this composition is considered as the one that delivers the best photovoltaic performances in the specific domain of Cu(2)ZnSnS(4)-based thin-film solar cells. The existence of this nonstoichiometric phase is definitely demonstrated here in an explicit and unequivocal manner on the basis of powder and single-crystal X-ray diffraction analyses coupled with electron microprobe analyses. Crystals are tetragonal, space group I ̅4, Z = 2, with a = 5.43440(15) Å and c = 10.8382(6) Å for Cu(2)ZnSnS(4) and a = 5.43006(5) Å and c = 10.8222(2) Å for Cu(1.71)Zn(1.18)Sn(0.99)S(4). © 2012 American Chemical Society

Electrical Study of Trapped Charges in Copper-Doped Zinc Oxide Films by Scanning Probe Microscopy for Nonvolatile Memory Applications

PubMed Central

Su, Ting; Zhang, Haifeng

2017-01-01

Charge trapping properties of electrons and holes in copper-doped zinc oxide (ZnO:Cu) films have been studied by scanning probe microscopy. We investigated the surface potential dependence on the voltage and duration applied to the copper-doped ZnO films by Kelvin probe force microscopy. It is found that the Fermi Level of the 8 at.% Cu-doped ZnO films shifted by 0.53 eV comparing to undoped ZnO films. This shift indicates significant change in the electronic structure and energy balance in Cu-doped ZnO films. The Fermi Level (work function) of zinc oxide films can be tuned by Cu doping, which are important for developing this functional material. In addition, Kelvin probe force microscopy measurements demonstrate that the nature of contact at Pt-coated tip/ZnO:Cu interface is changed from Schottky contact to Ohmic contact by increasing sufficient amount of Cu ions. The charge trapping property of the ZnO films enhance greatly by Cu doping (~10 at.%). The improved stable bipolar charge trapping properties indicate that copper-doped ZnO films are promising for nonvolatile memory applications. PMID:28135335

The effect of nano-TiO2 photocatalysis on the antioxidant activities of Cu, Zn-SOD at physiological pH.

PubMed

Zheng, Wen; Zou, Hai-Feng; Lv, Shao-Wu; Lin, Yan-Hong; Wang, Min; Yan, Fei; Sheng, Ye; Song, Yan-Hua; Chen, Jie; Zheng, Ke-Yan

2017-09-01

Security issues of nanoparticles on biological toxicity and potential environmental risk have attracted more and more attention with the rapid development and wide applications of nanotechnology. In this work, we explored the effect and probable mechanism of nano-TiO 2 on antioxidant activity of copper, zinc superoxide dismutase (Cu, Zn-SOD) under natural light and mixed light at physiological pH. Nano-TiO 2 was prepared by sol-hydrothermal method, and then characterized by X-ray Diffraction (XRD) and Transmission electron micrographs (TEM). The Cu, Zn-SOD was purified by sephadex G75 chromatography and qualitatively analyzed by sodium dodecyl sulfate polypropylene amide gel electrophoresis (SDS-PAGE). The effect and mechanism were elucidated base on Fourier Transform Infrared Spectrometer (FT-IR), Circular Dichroism (CD), zeta potential, and electron spin resonance (ESR) methods. Accompanying the results of FT-IR, CD and zeta potential, it could be concluded that nano-TiO 2 had no effect on the antioxidant activity of Cu, Zn-SOD by comparing the relative activity under natural light at physiological pH. But the relative activity of Cu, Zn-SOD significantly decreased along with the increase of nano-TiO 2 concentration under the mixed light. The results of ESR showed the cause of this phenomenon was the Cu(II) in the active site of Cu, Zn-SOD was reduced to Cu(I) by H 2 O 2 and decreased the content of active Cu, Zn-SOD. The reduction can be inhibited by catalase. Excess O 2 ·- produced by nano-TiO 2 photocatalysis under mixed light accumulated a mass of H 2 O 2 through disproportionation reaction in this experimental condition. The results show that nano-TiO 2 cannot affect the antioxidant activity of Cu, Zn-SOD in daily life. The study on the effect of nano-TiO 2 on Cu, Zn-SOD will provide a valid theory support for biological safety and the toxicological effect mechanism of nanomaterials on enzyme. Copyright © 2017 Elsevier B.V. All rights reserved.

Modification of a single tryptophan residue in human Cu,Zn-superoxide dismutase by peroxynitrite in the presence of bicarbonate.

PubMed

Yamakura, F; Matsumoto, T; Fujimura, T; Taka, H; Murayama, K; Imai, T; Uchida, K

2001-07-09

Human recombinant Cu,Zn-SOD was reacted with peroxynitrite in a reaction mixture containing 150 mM potassium phosphate buffer (pH 7.4) 25 mM sodium bicarbonate, and 0.1 mM diethylenetriamine pentaacetic acid. Disappearance of fluorescence emission at 350 nm, which could be attributed to modification of a single tryptophan residue, was observed in the modified enzyme with a pH optimum of around 8.4. A fluorescence decrease with the same pH optimum was also observed without sodium bicarbonate, but with less efficiency. Amino acid contents of the modified enzyme showed no significant difference in all amino acids except the loss of a single tryptophan residue of the enzyme. The peroxynitrite-modified enzyme showed an increase in optical absorption around 350 nm and 30% reduced enzyme activity based on the copper contents. The modified enzyme showed the same electron paramagnetic resonance spectrum as that of the control enzyme. The modified Cu,Zn-SOD showed a single protein band in sodium dodecyl sulfate--polyacrylamide gel electrophoresis (SDS--PAGE) and five protein bands in non-denaturing PAGE. From this evidence, we conclude that nitration and/or oxidation of the single tryptophan 32 and partial inactivation of the enzyme activity of Cu,Zn-SOD is caused by a peroxynitrite-carbon dioxide adduct without perturbation of the active site copper integrity.

Cu-Doped ZnO Thin Films Grown by Co-deposition Using Pulsed Laser Deposition for ZnO and Radio Frequency Sputtering for Cu

NASA Astrophysics Data System (ADS)

Shin, Hyun Wook; Son, Jong Yeog

2018-05-01

Cu-doped ZnO (CZO) thin films were fabricated on single-crystalline (0001) Al2O3 substrates by co-deposition using pulsed laser deposition for ZnO and radio frequency sputtering for Cu. CZO thin films with 0-20% molar concentrations are obtained by adjusting the deposition rates of ZnO and Cu. The CZO thin films exhibit room temperature ferromagnetism, and CZO with 5% Cu molar concentration has maximum remanent magnetization, which is consistent with theoretical results.

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

NASA Astrophysics Data System (ADS)

Siriwardane, Ranjani V.; Poston, James A.

1993-05-01

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

Response to Comment on “Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts”

DOE PAGES

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.; ...

2017-09-01

In their Comment on our recent paper, Nakamura et al. argue that our x-ray photoelectron spectroscopy (XPS) analysis was affected by the presence of formate species on the catalyst surface. This argument is not valid because the reactant gases were evacuated at temperatures from 525 to 575 kelvin, conditions under which formate is not stable on the catalyst surface. An analysis of the XPS results obtained after exposing zinc oxide/copper (111) [ZnO/Cu(111)] surfaces to hydrogen (H 2) and mixtures of carbon dioxide (CO 2)/H 2 show an absence of carbon (C) 1s signal, no asymmetries in the oxygen (O) 1smore » peak, and a Zn:O intensity close to 1:1. Thus and finally, the most active phase of these catalysts contained a ZnO-Cu interface.« less

ZnO/Cu(InGa)Se.sub.2 solar cells prepared by vapor phase Zn doping

DOEpatents

Ramanathan, Kannan; Hasoon, Falah S.; Asher, Sarah E.; Dolan, James; Keane, James C.

2007-02-20

A process for making a thin film ZnO/Cu(InGa)Se.sub.2 solar cell without depositing a buffer layer and by Zn doping from a vapor phase, comprising: depositing Cu(InGa)Se.sub.2 layer on a metal back contact deposited on a glass substrate; heating the Cu(InGa)Se.sub.2 layer on the metal back contact on the glass substrate to a temperature range between about 100.degree. C. to about 250.degree. C.; subjecting the heated layer of Cu(InGa)Se.sub.2 to an evaporant species from a Zn compound; and sputter depositing ZnO on the Zn compound evaporant species treated layer of Cu(InGa)Se.sub.2.

Novel dimeric interface and electrostatic recognition in bacterial Cu,Zn superoxide dismutase

PubMed Central

Bourne, Yves; Redford, Susan M.; Steinman, Howard M.; Lepock, James R.; Tainer, John A.; Getzoff, Elizabeth D.

1996-01-01

Eukaryotic Cu,Zn superoxide dismutases (CuZnSODs) are antioxidant enzymes remarkable for their unusually stable β-barrel fold and dimer assembly, diffusion-limited catalysis, and electrostatic guidance of their free radical substrate. Point mutations of CuZnSOD cause the fatal human neurodegenerative disease amyotrophic lateral sclerosis. We determined and analyzed the first crystallographic structure (to our knowledge) for CuZnSOD from a prokaryote, Photobacterium leiognathi, a luminescent symbiont of Leiognathid fish. This structure, exemplifying prokaryotic CuZnSODs, shares the active-site ligand geometry and the topology of the Greek key β-barrel common to the eukaryotic CuZnSODs. However, the β-barrel elements recruited to form the dimer interface, the strategy used to forge the channel for electrostatic recognition of superoxide radical, and the connectivity of the intrasubunit disulfide bond in P. leiognathi CuZnSOD are discrete and strikingly dissimilar from those highly conserved in eukaryotic CuZnSODs. This new CuZnSOD structure broadens our understanding of structural features necessary and sufficient for CuZnSOD activity, highlights a hitherto unrecognized adaptability of the Greek key β-barrel building block in evolution, and reveals that prokaryotic and eukaryotic enzymes diverged from one primordial CuZnSOD and then converged to distinct dimeric enzymes with electrostatic substrate guidance. PMID:8917495

Metal transport capabilities of anticancer copper chelators.

PubMed

Gaál, Anikó; Orgován, Gábor; Mihucz, Victor G; Pape, Ian; Ingerle, Dieter; Streli, Christina; Szoboszlai, Norbert

2018-05-01

In the present study, several Cu chelators [2,2'-biquinoline, 8-hydroxiquinoline (oxine), ammonium pyrrolidinedithiocarbamate (APDTC), Dp44mT, dithizone, neocuproine] were used to study Cu uptake, depletion and localization in different cancer cell lines. To better understand the concentration dependent fluctuations in the Cu intracellular metal content and Cu-dependent in vitro antiproliferative data, the conditional stability constants of the Cu complex species of the investigated ligands were calculated. Each investigated chelator increased the intracellular Cu content on HT-29 cells causing Cu accumulation depending on the amount of the free Cu(II). Copper accumulation was 159 times higher for Dp44mT compared to the control. Investigating a number of other transition metals, intracellular accumulation of Cd was observed only for two chelators. Intracellular Zn content slightly decreased (cca. 10%) for MCF-7 cells, while a dramatic decrease was observed on MDA-MB-231 ones (cca. 50%). A similar decrease was observed for HCT-116, while Zn depletion for HT-29 corresponded to cca. 20%. The IC 50 values were registered for the investigated four cell lines at increasing external Cu(II) concentration, namely, MDA-MB-231 cells had the lowest IC 50 values for Dp44mT ranging between 7 and 35 nM. Thus, Zn depletion could be associated with lower IC 50 values. Copper depletion was observed for all ligands being less pronounced for Dp44mT and neocuproine. Copper localization and its colocalization with Zn were determined by μ-XRF imaging. Loose correlation (0.57) was observed for the MCF-7 cells independently of the applied chelator. Similarly, a weak correlation (0.47) was observed for HT-29 cells treated with Cu(II) and oxine. Colocalization of Cu and Zn in the nucleus of HT-29 cells was observed for Dp44mT (correlation coefficient of 0.85). Copyright © 2018 Elsevier GmbH. All rights reserved.

Effects of the copper content on the structural and electrical properties of Cu2ZnSnSe4 bulks

NASA Astrophysics Data System (ADS)

Tsega, Moges; Dejene, F. B.; Koao, L. F.

2016-01-01

We have investigated the concept of defect in CuxZnSnSe4 (x=1.6-2.0) and Cuy(Zn0.9Sn1.1)Se4 (y= 1.6-2.0) bulks prepared by liquid-phase sintering at 600 °C for 2 h with soluble sintering aids of Sb2S3 and Te. All samples were found to exhibit p-type semiconductor for CuxZnSnSe4, while n-type of behavior obtained at y= 1.8-2.0 for Cuy(Zn0.9Sn1.1)Se4 pellets. The Cu vacancy acts as an acceptor point defect to form the p-type semiconductor, and Sn4+ acts as a donor to form the n-type behavior for the Sn-rich CZTSe. SEM images of pellets show dense surface morphology, and increase in grain size upon Cu inclusion. The largely increased Hall mobility and the slightly changed carrier concentration for Cuy(Zn0.9Sn1.1)Se4 with increasing the Cu content is related to the types of its defects. At y=2.0 with carrier concentration of 4.88×1017 cm-3 showed the highest mobility of around 58 cm2/V s. Based upon the proposed point defects, the CZTSe property can be consistently explained.

In vivo-folded metal-metallothionein 3 complexes reveal the Cu-thionein rather than Zn-thionein character of this brain-specific mammalian metallothionein.

PubMed

Artells, Ester; Palacios, Oscar; Capdevila, Mercè; Atrian, Sílvia

2014-03-01

Metallothionein-3 (MT3) is one of the four mammalian metallothioneins (MT), and is constitutively synthesized in the brain. MT3 acts both intracellularly and extracellularly in this organ, performing functions related to neuronal growth and physiological metal (Zn and Cu) handling. It appears to be involved in the prevention of neurodegenerative disorders caused by insoluble Cu-peptide aggregates, as it triggers a Zn-Cu swap that may counteract the deleterious presence of copper in neural tissues. The literature data on MT3 coordination come from studies either on apo-MT3 reconstitution or the reaction of Zn-MT3 with Cu(2+) , an ion that is hardly present inside cells. To ascertain the MT3 metal-binding features in a scenario closer to the reductive cell cytoplasm, a study of the recombinant Zn(2+) , Cd(2+) and Cu(+) complexes of MT3, βMT3, and αMT3, as well as the in vitro Zn(2+) -Cd(2+) and Zn(2+) -Cu(+) replacement processes, is presented here. We conclude that MT3 has a Cu-thionein character that is stronger than that of the MT1 and MT2 isoforms - also present in the mammalian brain - which is mainly contributed by its β domain. In contrast, the α domain retains a high capacity to bind Zn(2+) ions, and, consequently, the entire MT3 peptide shows a peculiar dual ability to handle both metal ions. The nature of the formed Cu(+) -MT3 complexes oscillates from heterometallic Cu6 Zn4 -MT3 to homometallic Cu10 -MT3 major species, in a narrow Cu concentration range. Therefore, the entire MT3 peptide shows a high capacity to bind Cu(+) , provided that this occurs in a nonoxidative milieux. This reflects a peculiar property of this MT isoform, which accurately senses different Cu contents in the environment in which it is synthesized. © 2014 FEBS.

Rapid, controllable, one-pot and room-temperature aqueous synthesis of ZnO:Cu nanoparticles by pulsed UV laser and its application for photocatalytic degradation of methyl orange.

PubMed

Arabi, Mozhgan; Baizaee, Seyyed Mahdy; Bahador, Alireza; Otaqsara, Seyed Mohammad Taheri

2018-05-01

Zinc oxide (ZnO) and ZnO:Cu nanoparticles (NPs) were synthesized using a rapid, controllable, one-pot and room-temperature pulsed UV-laser assisted method. UV-laser irradiation was used as an effective energy source in order to gain better control over the NPs size and morphology in aqueous media. Parameters effective in laser assisted synthesis of NPs such as irradiation time and laser shot repetition rate were optimized. Photoluminescence (PL) spectra of ZnO NPs showed a broad emission with two trap state peaks located at 442 and 485 nm related to electronic transition from zinc interstitial level (I Zn ) to zinc vacancy level (V Zn ) and electronic transition from conduction band to the oxygen vacancy level (V O ), respectively. For ZnO:Cu NPs, trap state emissions disappeared completely and a copper (Cu)-related emission appeared. PL intensity of Cu-related emission increased with the increase in concentration of Cu 2+ , so that for molar ratio of Cu:Zn 2%, optimal value of PL intensity was obtained. The photocatalytic activity of Cu-doped ZnO revealed 50 and 100% increasement than that of undoped NPs under UV and visible irradiation, respectively. The enhanced photocatalytic activity could be attributed to smaller crystal size, as well as creation of impurity acceptor levels (T 2 ) inside the ZnO energy band gap. Copyright © 2017 John Wiley & Sons, Ltd.

Cu-doped Cd1- x Zn x S alloy: synthesis and structural investigations

NASA Astrophysics Data System (ADS)

Yadav, Indu; Ahlawat, Dharamvir Singh; Ahlawat, Rachna

2016-03-01

Copper doped Cd1- x Zn x S ( x ≤ 1) quantum dots have been synthesized using chemical co-precipitation method. Structural investigation of the synthesized nanomaterials has been carried out by powder XRD method. The XRD results have confirmed that as-prepared Cu-doped Cd1- x Zn x S quantum dots have hexagonal structure. The average nanocrystallite size was estimated in the range 2-12 nm using Debye-Scherrer formula. The lattice constants, lattice plane, d-spacing, unit cell volume, Lorentz factor and dislocation density were also calculated from XRD data. The change in particle size was observed with the change in Zn concentration. Furthermore, FTIR spectra of the prepared samples were observed for identification of COO- and O-H functional groups. The TEM study has also reported the same size range of nanoparticles. The increase in agglomeration has been observed with the increase in Zn concentration in the prepared samples.

Chemical behavior of Cu, Zn, Cd, and Pb in a eutrophic reservoir: speciation and complexation capacity.

PubMed

Tonietto, Alessandra Emanuele; Lombardi, Ana Teresa; Choueri, Rodrigo Brasil; Vieira, Armando Augusto Henriques

2015-10-01

This research aimed at evaluating cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) speciation in water samples as well as determining water quality parameters (alkalinity, chlorophyll a, chloride, conductivity, dissolved organic carbon, dissolved oxygen, inorganic carbon, nitrate, pH, total suspended solids, and water temperature) in a eutrophic reservoir. This was performed through calculation of free metal ions using the chemical equilibrium software MINEQL+ 4.61, determination of labile, dissolved, and total metal concentrations via differential pulse anodic stripping voltammetry, and determination of complexed metal by the difference between the total concentration of dissolved and labile metal. Additionally, ligand complexation capacities (CC), such as the strength of the association of metals-ligands (logK'ML) and ligand concentrations (C L) were calculated via Ruzic's linearization method. Water samples were taken in winter and summer, and the results showed that for total and dissolved metals, Zn > Cu > Pb > Cd concentration. In general, higher concentrations of Cu and Zn remained complexed with the dissolved fraction, while Pb was mostly complexed with particulate materials. Chemical equilibrium modeling (MINEQL+) showed that Zn(2+) and Cd(2+) dominated the labile species, while Cu and Pb were complexed with carbonates. Zinc was a unique metal for which a direct relation between dissolved species with labile and complexed forms was obtained. The CC for ligands indicated a higher C L for Cu, followed by Pb, Zn, and Cd in decreasing amounts. Nevertheless, the strength of the association of all metals and their respective ligands was similar. Factor analysis with principal component analysis as the extraction procedure confirmed seasonal effects on water quality parameters and metal speciation. Total, dissolved, and complexed Cu and total, dissolved, complexed, and labile Pb species were all higher in winter, whereas in summer, Zn was mostly present in the

Compositional ratio effect on the surface characteristics of CuZn thin films

NASA Astrophysics Data System (ADS)

Choi, Ahrom; Park, Juyun; Kang, Yujin; Lee, Seokhee; Kang, Yong-Cheol

2018-05-01

CuZn thin films were fabricated by RF co-sputtering method on p-type Si(100) wafer with various RF powers applied on metallic Cu and Zn targets. This paper aimed to determine the morphological, chemical, and electrical properties of the deposited CuZn thin films by utilizing a surface profiler, atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), UV photoelectron spectroscopy (UPS), and a 4-point probe. The thickness of the thin films was fixed at 200 ± 8 nm and the roughness of the thin films containing Cu was smaller than pure Zn thin films. XRD studies confirmed that the preferred phase changed, and this tendency is dependent on the ratio of Cu to Zn. AES spectra indicate that the obtained thin films consisted of Cu and Zn. The high resolution XPS spectra indicate that as the content of Cu increased, the intensities of Zn2+ decreased. The work function of CuZn thin films increased from 4.87 to 5.36 eV. The conductivity of CuZn alloy thin films was higher than pure metallic thin films.

Phase Equilibria in the ZnO-"FeO"-SiO2 System in Reducing Atmosphere and in the ZnO-"FeO"-SiO2-"Cu2O" System in Equilibrium with Liquid Copper Metal at 1250 °C (1523 K)

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Hayes, Peter C.; Jak, Evgueni

2018-05-01

Recent experimental studies in the ZnO-"FeO"-SiO2 system in reducing atmosphere demonstrated significant discrepancies with the current FactSage thermodynamic model developed using previous experimental data in this system in equilibrium with metallic iron and air. The present experimental study on phase equilibria in the ZnO-"FeO"-SiO2-"Cu2O" system in equilibrium with liquid copper at 1250 °C (1523 K) at low copper oxide concentrations in slag was initiated and undertaken to resolve these discrepancies. A high-temperature equilibration-rapid quenching-electron-probe X-ray microanalysis (EPMA) technique using a primary phase substrate support and closed system approach with Cu metal introduced to determine effective equilibrium oxygen partial pressure from the Cumetal/Cu2Oslag equilibria was applied to provide accurate information on the liquidus and corresponding solid compositions in the spinel, willemite, and tridymite primary phase fields. The present results confirmed the accuracy of the FactSage model, resolved discrepancies, and demonstrated significant uncertainties in the recent studies by other authors on the system in the open reducing atmosphere. The present study shows how this closed system approach can be used to obtain key thermodynamic data on phase equilibria in systems containing volatile metal species, overcoming the limitations and uncertainties encountered in conventional open gas/condensed phase equilibration with these systems. The study highlights the importance of the focus on obtaining accurate experimental data and the risks of misleading information from inadequate experimental control and analysis. The study also demonstrates that continuing in-depth critical review and analysis of the elemental reactions taking place in complex systems is an essential step in phase equilibrium research.

A porous Cu/LDPE composite for copper-containing intrauterine contraceptive devices.

PubMed

Zhang, Weiwei; Xia, Xianping; Qi, Cheng; Xie, Changsheng; Cai, Shuizhou

2012-02-01

To improve the rates of both cupric ion release and the utilization of copper in non-porous copper/low-density polyethylene (Cu/LDPE) composite, a porous Cu/LDPE composite is proposed and developed in the present work. Here 2,5-di-tert-butylhydroquinone was chosen as the porogen, ethyl acetate was chosen as the solvent for extraction, and the porous Cu/LDPE composite was obtained by using injection molding and the particulate leaching method. After any residual ethyl acetate remaining inside the porous Cu/LDPE composite had been removed by vacuum drying, the composite was characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry and absorption measurement. For comparison, a non-porous Cu/LDPE composite was also characterized in the same way. The results show that the porous structure was successfully introduced into the polymeric base of the non-porous Cu/LDPE composite, and the porous Cu/LDPE composite is a simple hybrid of copper particles and porous LDPE. The results also show that the introduction of a porous structure can improve the cupric ion release rate of the non-porous Cu/LDPE composite with a certain content of copper particles, indicating that the utilization rate of copper can be improved either the introduction of a porous structure, and that the porous Cu/LDPE composite is another promising material for copper-containing intrauterine devices. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Comparison of serum Concentration of Se, Pb, Mg, Cu, Zn, between MS patients and healthy controls

PubMed Central

Alizadeh, Anahita; Mehrpour, Omid; Nikkhah, Karim; Bayat, Golnaz; Espandani, Mahsa; Golzari, Alireza; Jarahi, Lida; Foroughipour, Mohsen

2016-01-01

Introduction Multiple Sclerosis (MS) is defined as one of the inflammatory autoimmune disorders and is common. Its exact etiology is unclear. There are some evidences on the role of environmental factors in susceptible genetics. The aim of this study is to evaluate the possible role of Selenium, Zinc, Copper, Lead and Magnesium metals in Multiple Sclerosis patients. Methods In the present analytical cross-sectional study, 56 individuals including 26 patients and 30 healthy controls were enrolled in the evaluation. The serum level of Se, Zn, Cu, Pb were quantified in graphite furnace conditions and flame conditions by utilizing an atomic absorption Perkin Elmer spectrophotometer 3030. The serum levels of Mg were measured by auto analyzer 1500 BT. The mean level of minerals (Zn, Pb, Cu, Mg, Se) in serum samples were compared in both cases and controls. The mean level of minerals (Zn, Pb, Cu, Mg, Se) in serum samples were compared in both cases and controls by using independent-samples t-test for normal distribution and Mann-Whitney U test as a non-parametric test. All statistical analyses were carried out using SPSS 11.0. Results As well as the Zn, Cu, and Se, there was no significant difference between MS patients and healthy individuals in Pb concentrations (p-value = 0.11, 0.14, 0.32, 0.20 respectively) but the level of Mg was significantly different (p= 0.001). Conclusion All serum concentrations of Zn, Pb, Se, Cu in both groups were in normal ranges and there was no difference in MS patients compared with the healthy group who were matched in genetics. Blood level of Mg was significantly lower in MS patients. But it should be noted that even with the low level of serum magnesium in MS patients, this value is still in the normal range. PMID:27757186

Preparation and Optoelectronic Characteristics of ZnO/CuO-Cu2O Complex Inverse Heterostructure with GaP Buffer for Solar Cell Applications

PubMed Central

Hsu, Chih-Hung; Chen, Lung-Chien; Lin, Yi-Feng

2013-01-01

This study reports the optoelectronic characteristics of ZnO/GaP buffer/CuO-Cu2O complex (COC) inverse heterostructure for solar cell applications. The GaP and COC layers were used as buffer and absorber in the cell structure, respectively. An energy gap widening effect and CuO whiskers were observed as the copper (Cu) layer was exerted under heat treatment for oxidation at 500 °C for 10 min, and arose from the center of the Cu2O rods. For preparation of the 30 nm-thick GaP buffer by sputtering from GaP target, as the nitrogen gas flow rate increased from 0 to 2 sccm, the transmittance edge of the spectra demonstrated a blueshift form 2.24 to 3.25 eV. Therefore, the layer can be either GaP, GaNP, or GaN by changing the flow rate of nitrogen gas. PMID:28788341

Structural and optical properties of pure and copper doped zinc oxide nanoparticles

NASA Astrophysics Data System (ADS)

Sajjad, Muhammad; Ullah, Inam; Khan, M. I.; Khan, Jamshid; Khan, M. Yaqoob; Qureshi, Muhammad Tauseef

2018-06-01

Pure and copper-doped zinc oxide nanoparticles (NPs) have been synthesized via chemical co-precipitation method where hydrazine is used as reducing agent and aqueous extract of Euphorbia milii plant as capping agent. Main objectives of the reported work are to investigate the effect of copper doping on crystal structure of ZnO nanoparticles; to study the effect of copper doping on optical band gap of ZnO nanoparticles and photoluminescence (PL) study of pure and copper-doped ZnO nanoparticles. To achieve the aforementioned objectives, XRD and SEM tests were performed for the identification and confirmation of crystal structure and morphology of the prepared samples. From XRD data the average grain size for pure ZnO was observed to be 24.62 nm which was first decreased to 18.95 nm for 5 wt% Cu-doped sample and then it was found to increase up to 37.80 nm as the Cu doping was increased to 7 wt%. Optical band gap of pure and Cu-doped ZnO nanoparticles was calculated from diffuse reflectance spectroscopy (DRS) spectra and was found to decrease from 3.13 eV to 2.94 eV as the amount of Cu increases up to 7 wt%. In photoluminescence study, PL technique was used and enhanced visible spectrum was observed. For further characterization FT-IR and EDX tests were also carried out.

Cooperative cytotoxic activity of Zn and Cu in bovine serum albumin-conjugated ZnS/CuS nano-composites in PC12 cancer cells

NASA Astrophysics Data System (ADS)

Wang, Hua-Jie; Yu, Xue-Hong; Wang, Cai-Feng; Cao, Ying

2013-11-01

Series of self-assembled and mono-dispersed bovine serum albumin (BSA)-conjugated ZnS/CuS nano-composites with different Zn/Cu ratios had been successfully synthesized by a combination method of the biomimetic synthesis and ion-exchange strategy under the gentle conditions. High-resolution transmission electron microscopy observation, Fourier transform infrared spectra and zeta potential analysis demonstrated that BSA-conjugated ZnS/CuS nano-composites with well dispersity had the hierarchical structure and BSA was a key factor to control the morphology and surface electro-negativity of final products. The real-time monitoring by atomic absorption spectroscopy and powder X-ray diffraction revealed that the Zn/Cu ratio of nano-composites could be controlled by adjusting the ion-exchange time. In addition, the metabolic and morphological assays indicated that the metabolic proliferation and spread of rat pheochromocytoma (PC12) cells could be inhibited by nano-composites, with the high anti-cancer activity at a low concentration (4 ppm). What were more important, Zn and Cu in nano-composites exhibited a positive cooperativity at inhibiting cancer cell functions. The microscope observation and biochemical marker analysis clearly revealed that the nano-composites-included lipid peroxidation and disintegration of membrane led to the death of PC12 cells. Summarily, the present study substantiated the potential of BSA-conjugated ZnS/CuS nano-composites as anti-cancer drug.

Atmospheric emissions of Cu and Zn from coal combustion in China: Spatio-temporal distribution, human health effects, and short-term prediction.

PubMed

Li, Rui; Li, Junlin; Cui, Lulu; Wu, Yu; Fu, Hongbo; Chen, Jianmin; Chen, Mindong

2017-10-01

China has become the largest coal consumer and important emitter of trace metals in the world. A multiple-year inventory of atmospheric copper (Cu) and zinc (Zn) emissions from coal combustion in 30 provinces of China and 4 economic sectors (power plant, industry sector, residential sector, and others) for the period of 1995-2014 has been calculated. The results indicated that the total emissions of Cu and Zn increased from 5137.70 t and 11484.16 t in 1995-7099.24 t and 14536.61 t in 2014, at an annual average growth rate of 1.90% and 1.33%, respectively. The industrial sector ranked as the leading source, followed by power plants, the residential use, and other sectors. The emissions of Cu and Zn were predominantly concentrated in the northern and eastern regions of China due to the enormous consumption of coal by the industrial and the power sectors. The emissions of Cu and Zn were closely associated with mortality and life expectancy (LE) on the basis of multiple regression analysis. Spatial econometric models suggested that Cu and Zn emissions displayed significantly positive relevance with mortality, while they exhibited negative correlation with LE. The influence of the Cu emission peaked in the north of China for both mortality and LE, while the impacts of the Zn emission on mortality and LE reached a maximum value in Xinjiang Province. The results of the grey prediction model suggested that the Cu emission would decrease to 5424.73 t, whereas the Zn emissions could reach 17402.13 t in 2020. Analysis of more specific data are imperative in order to estimate the emissions of both metals, to assess their human health effects, and then to adopt effective measures to prevent environmental pollution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biological diversity of Salix taxa in Cu, Pb and Zn phytoextraction from soil.

PubMed

Mleczek, Mirosław; Rutkowski, Paweł; Goliński, Piotr; Kaczmarek, Zygmunt; Szentner, Kinga; Waliszewska, Bogusława; Stolarski, Mariusz; Szczukowski, Stefan

2017-02-01

The aim of the study was to estimate the efficiency of copper (Cu), lead (Pb) and zinc (Zn) phytoextraction by 145 Salix taxa cultivated in an area affected by industrial activity. Survivability and biomass of plants were also analyzed. The highest Cu, Pb and Zn content in shoots was 33.38 ± 2.91 (S. purpurea × viminalis 8), 24.64 ± 1.97 (S. fragilis 1) and 58.99 ± 4.30 (S. eriocephala 7) mg kg -1 dry weight, respectively. In the case of unwashed leaves, the highest content of these metals was 135.06 ± 8.14 (S. purpurea 26), 67.98 ± 5.27 (S. purpurea 45) and 142.56 ± 12.69 (S. alba × triandra 2) mg kg -1 dw, while in washed leaves it was 106.02 ± 11.12 (S. purpurea 45), 55.06 ± 5.75 (S. purpurea 45) and 122.87 ± 12.33 (S. alba × triandra 2) mg kg -1 dw, respectively. The differences between the highest and lowest values for Cu, Pb and Zn were 545%, 20500% and 535% in shoots; 2692%, 2560% and 7500% in unwashed leaves; and 3286%, 2221% and 6950% in washed leaves, respectively. S. acutifolia was able to effectively accumulate all three metals jointly, producing shoots that were well developed in both length and diameter when compared with the other tested willows-an ability that would suggest its high suitability for practical application.

Metal (Cu, Cd and Zn) removal and stabilization during multiple soil washing by saponin.

PubMed

Gusiatin, Zygmunt Mariusz; Klimiuk, Ewa

2012-01-01

The influence of multiple saponin washing on copper, cadmium and zinc removal and stability in three types of soils (loamy sand, loam, silty clay) was investigated. Distribution of metals and their mobility measured as the ratio of exchangeable form to the sum of all fractions in soils was differential. After single washing the highest efficiency of metal removal was obtained in loamy sand (82-90%) and loam (67-88%), whereas the lowest in silty clay (39-62%). In loamy sand and loam metals had higher mobility factors (44-61% Cu, 60-76% Cd, and 68-84% Zn) compared to silty clay (9% Cu, 28% Cd and 36% Zn). Triplicate washing led to increase both efficiency of metal removal and percentage content of their stable forms. In consequence, fractional patterns for metals before and after treatment changed visibly as a result of their redistribution. Based on the redistribution index, the most stable metal (mainly in residual and organic fractions) after triplicate washing was Cu in loamy sand and loam. For silty clay contaminated with Cd, effective metal removal and its stabilization required a higher number of washings. Copyright © 2011 Elsevier Ltd. All rights reserved.

Synthesis of graphene oxide-copper molybdate (GO-CuM) nanocomposites for photocatalytic application

NASA Astrophysics Data System (ADS)

Singh, Gajendar; Bhargava, V. Sai; Sharma, Manu

2018-05-01

Transition metal molybdates (TMBs) MMoO4 (M=Ni, Cu, Fe, Zn, Co, etc.) based nanocomposites have been considered as remarkable materials in the field of electronics, optics, catalysis, supercapicitors and energy storage devices. Nanocomposites of TMBs with graphene oxide have also been chosen as an effective material in photocatalytic application. GO-CuM nanocomposites were synthesized by ultra-sonication method at RT, followed by reflux route for preparation of CuM and GO by modified Hemmer's method. As prepared nanocomposites were characterized using analytical techniques such as PXRD, SEM, FT-IR and UV-Visible spectroscopy. The enhanced photocatalytic activity of Methylene blue (MB) dye was observed by GO-CuM nanocomposites as compared to pure copper molybdate. GO-CuM nanocomposites show high photodegradation rate (0.094 min-1) whereas CuM was degraded only 30 % with the rate of 0.0029 min-1. The high photocatalytic efficiency is due to the presence of graphene oxide that helps to delay the charge recombination in photocatalytic reaction The effect of the different amount of graphene oxide on the photocatalytic activity of as prepared photocatalyst has also been investigated.

Outstanding features of Cu-doped ZnS nanoclusters

NASA Astrophysics Data System (ADS)

Tawfik, Wael Z.; Farghali, A. A.; Moneim, Ahmed; Imam, N. G.; El-Dek, S. I.

2018-05-01

ZnS and their Cu-doped nanoclusters (NCs) were synthesized successfully using the wet chemical route with different Cu content. The crystalline structure was investigated using x-ray powder diffraction which assured the single-phase formation in cubic symmetry. High-resolution transmission electron microscope indicated the microstructure of NCs with a size ranging from 2–4 nm. A butterfly hysteresis (M-H) loop was observed at room temperature with large values of coercivity for the Cu content of x = 0.05. Photoluminescence emission spectra were recorded from 500–615 nm for pure and Cu-doped ZnS NCs at a 350 nm excitation wavelength. The sample exhibited green fluorescence bands peaking at 535, 544, 552.5, 558.2, and 560.6 nm, which confirmed the characteristic feature of Zn2+ as luminescent centers in the lattice. The additional yellow and orange emissions are due to defect levels or/and impurity centers. The dielectric constant as well as the conductivity values increased with increasing Cu content.

Surface study of films formed on copper and brass at open circuit potential

NASA Astrophysics Data System (ADS)

Procaccini, R.; Schreiner, W. H.; Vázquez, M.; Ceré, S.

2013-03-01

The corrosion resistance of Cu-Zn alloys strongly depends on the quality of the protective passive film. This study focuses on the influence of Zn on the composition of oxide films on copper and brass (Cu77Zn21Al2) in borax 0.1 mol L-1 (pH 9.2) solution, where the solubility of copper oxides is minimal. The effect of the presence of chloride ions at low concentration (0.01 mol L-1) in the electrolyte was also evaluated. Both conditions were studied using a set of different electrochemical, optical and surface techniques such as cyclic voltammetry, differential reflectance, X-ray photoelectron spectroscopy and Raman spectroscopy. A duplex Cu2O/CuO layer forms on copper at potentials positive to the open circuit potential (OCP), while in the case of brass, zinc compounds are also incorporated to the surface film. It also became evident that a surface film can be formed on these materials even at potentials negative to the OCP. Zn(II) species are the main constituents of the films growing on brass, while copper oxides are incorporated to the surface film when approaching the OCP. The presence of chloride ions at low concentrations contributes to the dissolution of the oxo-hydroxides formed during the early stages of the aging process at open circuit potential. Also, copper chloro-compounds are formed, as shown by Raman spectroscopy for both copper and brass electrodes.

A selective potentiometric copper (II) ion sensor based on the functionalized ZnO nanorods.

PubMed

Khun, K; Ibupoto, Z H; Liu, X; Nur, O; Willander, M; Danielsson, B

2014-09-01

In this work, ZnO nanorods were hydrothermally grown on the gold-coated glass substrate and characterized by field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) techniques. The ZnO nanorods were functionalized by two different approaches and performance of the sensor electrode was monitored. Fourier transform infrared spectroscopy (FTIR) was carried out for the confirmation of interaction between the ionophore molecules and ZnO nanorods. In addition to this, the surface of the electrode was characterized by X-ray photoelectron spectroscopy (XPS) showing the chemical and electronic state of the ionophore and ZnO nanorod components. The ionophore solution was prepared in the stabilizer, poly vinyl chloride (PVC) and additives, and then functionalized on the ZnO nanorods that have shown the Nernstian response with the slope of 31 mV/decade. However, the Cu2+ ion sensor was fabricated only by immobilizing the selective copper ion ionophore membrane without the use of PVC, plasticizers, additives and stabilizers and the sensor electrode showed a linear potentiometric response with a slope of 56.4 mV/decade within a large dynamic concentration range (from 1.0 x 10(-6) to 1.0 x 10(-1) M) of copper (II) nitrate solutions. The sensor showed excellent repeatability and reproducibility with response time of less than 10 s. The negligible response to potentially interfering metal ions such as calcium (Ca2+), magnesium (Mg2+), potassium (K+), iron (Fe3+), zinc (Zn2+), and sodium (Na+) allows this sensor to be used in biological studies. It may also be used as an indicator electrode in the potentiometric titration.

Development of two-step process for enhanced biorecovery of Cu-Zn-Ni from computer printed circuit boards.

PubMed

Shah, Monal B; Tipre, Devayani R; Purohit, Mamta S; Dave, Shailesh R

2015-08-01

Metal pollution due to the huge electronic waste (E-waste) accumulation is widespread across the globe. Extraction of copper, zinc and nickel from computer printed circuit boards (c-PCB) with a two-step bleaching process using ferric sulphate generated by Leptospirillum ferriphilum dominated consortium and the factors influencing the process were investigated in the present study. The studied factors with 10 g/L pulp density showed that pH 2.0 was optimum which resulted in 87.50-97.80% Cu-Zn-Ni extraction. Pre-treatment of PCB powder with acidified distilled water and NaCl solution showed 3.80-7.98% increase in metal extraction corresponding to 94.08% Cu, 99.80% Zn and 97.99% Ni extraction. Particle size of 75 μm for Cu and Zn while 1680 μm for Ni showed 2-folds increase in metal extraction, giving 97.35-99.80% Cu-Zn-Ni extraction in 2-6 days of reaction time. Whereas; 2.76-3.12 folds increase in Cu and Zn extraction was observed with the addition of 0.1% chelating agents. When the studies were carried out with high pulp density, ferric iron concentration of 16.57 g/L was found to be optimum for metal extraction from 75 g/L c-PCB and c-PCB addition in multiple installments resulted in 8.81-26.35% increase in metal extraction compared to single addition. The studied factors can be implemented for the scale-up aimed at faster recovery of multimetals from E-waste and thereby providing a secondary source of metal in an eco-friendly manner. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

The effect of copper, chromium, and zirconium on the microstructure and mechanical properties of Al-Zn-Mg-Cu alloys

NASA Technical Reports Server (NTRS)

Wagner, John A.; Shenoy, R. N.

1991-01-01

The present study evaluates the effect of the systematic variation of copper, chromium, and zirconium contents on the microstructure and mechanical properties of a 7000-type aluminum alloy. Fracture toughness and tensile properties are evaluated for each alloy in both the peak aging, T8, and the overaging, T73, conditions. Results show that dimpled rupture essentially characterize the fracture process in these alloys. In the T8 condition, a significant loss of toughness is observed for alloys containing 2.5 pct Cu due to the increase in the quantity of Al-Cu-Mg-rich S-phase particles. An examination of T8 alloys at constant Cu levels shows that Zr-bearing alloys exhibit higher strength and toughness than the Cr-bearing alloys. In the T73 condition, Cr-bearing alloys are inherently tougher than Zr-bearing alloys. A void nucleation and growth mechanism accounts for the loss of toughness in these alloys with increasing copper content.

Switching mechanism transition induced by annealing treatment in nonvolatile Cu/ZnO/Cu/ZnO/Pt resistive memory: From carrier trapping/detrapping to electrochemical metallization

NASA Astrophysics Data System (ADS)

Yang, Y. C.; Pan, F.; Zeng, F.; Liu, M.

2009-12-01

ZnO/Cu/ZnO trilayer films sandwiched between Cu and Pt electrodes were prepared for nonvolatile resistive memory applications. These structures show resistance switching under electrical bias both before and after a rapid thermal annealing (RTA) treatment, while it is found that the resistive switching effects in the two cases exhibit distinct characteristics. Compared with the as-fabricated device, the memory cell after RTA demonstrates remarkable device parameter improvements including lower threshold voltages, lower write current, and higher Roff/Ron ratio. A high-voltage forming process is avoided in the annealed device as well. Furthermore, the RTA treatment has triggered a switching mechanism transition from a carrier trapping/detrapping type to an electrochemical-redox-reaction-controlled conductive filament formation/rupture process, as indicated by different features in current-voltage characteristics. Both scanning electron microscopy observations and Auger electron spectroscopy depth profiles reveal that the Cu charge trapping layer in ZnO/Cu/ZnO disperses uniformly into the storage medium after RTA, while x-ray diffraction and x-ray photoelectron spectroscopy analyses demonstrate that the Cu atoms have lost electrons to become Cu2+ ions after dispersion. The above experimental facts indicate that the altered status of Cu in the ZnO/Cu/ZnO trilayer films during RTA treatment should be responsible for the switching mechanism transition. This study is envisioned to open the door for understanding the interrelation between different mechanisms that currently exist in the field of resistive memories.

Facile synthesis of Cu/tetrapod-like ZnO whisker compounds with enhanced photocatalytic properties

NASA Astrophysics Data System (ADS)

Liu, Hong; Liu, Huarong; Fan, Ximei

2017-09-01

Cu/tetrapod-like ZnO whisker (T-ZnOw) compounds were successfully synthesized using N2H4 \\cdot H2O as a reducing agent by a simple reduction method without any insert gas at room temperature. The crystal phase composition and morphology of the as-prepared samples were investigated by XRD, SEM and FESEM tests. The photocatalytic property of the as-prepared samples was detected by the degradation of methyl orange (MO) aqueous solution under UV irradiation. It can be found that Cu nanoparticles (CuNPs) dispersed on the surface of T-ZnOw increased with the increasing of Cu/Zn molar ratios (Cu/Zn MRs), and an octahedral structure of CuNPs was obtained when the sample was prepared with less than and equal to 7.30% Cu/Zn MR, but tended to a spherical or nanorod structure of CuNPs densely arranged on the surface of T-ZnOw, which is prepared by Cu/Zn MRs up to 22.00%. All the compounds exhibited excellent photocatalytic activity in decomposing of MO than T-ZnOw, the photocatalytic property of the samples increased with the increasing of Cu/Zn MRs up to 7.30%, while it decreases when further increasing the Cu/Zn MRs. The Schottky barrier of the Cu/T-ZnOw compound can effectively capture photoinduced electrons from the interface and enhanced the photocatalytic property of T-ZnOw.

Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

PubMed

Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

2013-06-25

Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

Photoluminescence of vapor and solution grown ZnTe single crystals

NASA Astrophysics Data System (ADS)

Biao, Y.; Azoulay, M.; George, M. A.; Burger, A.; Collins, W. E.; Silberman, E.; Su, C.-H.; Volz, M. E.; Szofran, F. R.; Gillies, D. C.

1994-04-01

ZnTe single crystals grown by horizontal physical vapor transport (PVT) and by vertical traveling heater method (THM) from a Te solution were characterized by photoluminescence (PL) at 10.6 K and by atomic force microscopy (AFM). Copper was identified by PL as a major impurity existing in both crystals, forming a substitutional acceptor, Cu Zn. The THM ZnTe crystals were found to contain more Cu impurity than the PVT ZnTe crystals. The formation of Cu Zn-V Te complexes and the effects of annealing, oxygen contamination and intentional Cu doping were also studied. Finally, the surface morphology analyzed by AFM was correlated to the PL results.

Arbuscular mycorrhiza alters metal uptake and the physiological response of Coffea arabica seedlings to increasing Zn and Cu concentrations in soil.

PubMed

Andrade, S A L; Silveira, A P D; Mazzafera, P

2010-10-15

Studies on mycorrhizal symbiosis effects on metal accumulation and plant tolerance are not common in perennial crops under metal stress. The objective of this study was to evaluate the influence of mycorrhization on coffee seedlings under Cu and Zn stress. Copper (Cu) and zinc (Zn) uptake and some biochemical and physiological traits were studied in thirty-week old Coffea arabica seedlings, in response to the inoculation with arbuscular mycorrhizal fungi (AMF) and to increasing concentrations of Cu or Zn in soil. The experiments were conducted under greenhouse conditions in a 2×4 factorial design (inoculation or not with AMF and 0, 50, 150 and 450mgkg(-1) Cu or 0, 100, 300 and 900mgkg(-1) Zn). Non-mycorrhizal plants maintained a hampered and slow growth even in a soil with appropriate phosphorus (P) levels for this crop. As metal levels increased in soil, a greater proportion of the total absorbed metals were retained by roots. Foliar Cu concentrations increased only in non-mycorrhizal plants, reaching a maximum concentration of 30mgkg(-1) at the highest Cu in soil. Mycorrhization prevented the accumulation of Cu in leaves, and mycorrhizal plants showed higher Cu contents in stems, which indicated a differential Cu distribution in AMF-associated or non-associated plants. Zn distribution and concentrations in different plant organs followed a similar pattern independently of mycorrhization. In mycorrhizal plants, only the highest metal concentrations caused a reduction in biomass, leading to significant changes in some biochemical indicators, such as malondialdehyde, proline and amino acid contents in leaves and also in foliar free amino acid composition. Marked differences in these physiological traits were also found due to mycorrhization. In conclusion, AMF protected coffee seedlings against metal toxicity. Copyright © 2010 Elsevier B.V. All rights reserved.

First-principles study of defect formation in a photovoltaic semiconductor Cu2ZnGeSe4

NASA Astrophysics Data System (ADS)

Nishihara, Hironori; Maeda, Tsuyoshi; Wada, Takahiro

2018-02-01

The formation energies of neutral Cu, Zn, Ge, and Se vacancies in kesterite-type Cu2ZnGeSe4 were evaluated by first-principles pseudopotential calculations using plane-wave basis functions. The calculations were performed at typical points in Cu-(Zn1/2Ge1/2)-Se and Cu3Se2-ZnSe-GeSe2 pseudoternary phase diagrams for Cu2ZnGeSe4. The results were compared with those for Cu2ZnSnSe4, Cu2ZnGeS4, and Cu2ZnSnS4 calculated using the same version of the CASTEP program code. The results indicate that Cu vacancies are easily formed in Cu2ZnGeSe4 under the Cu-poor condition as in the above compounds and CuInSe2, suggesting that Cu2ZnGeSe4 is also a preferable p-type absorber material for thin-film solar cells. The formation energies of possible antisite defects, such as CuZn and CuGe, and of possible complex defects, such as CuZn+ZnCu, were also calculated and compared within the above materials. The antisite defect of CuZn, which has the smallest formation energy within the possible defects, is concluded to be the most hardly formed in Cu2ZnGeSe4 among the compounds.

Antibacterial activity of trimetal (CuZnFe) oxide nanoparticles.

PubMed

Alzahrani, Khalid E; Niazy, Abdurahman A; Alswieleh, Abdullah M; Wahab, Rizwan; El-Toni, Ahmed M; Alghamdi, Hamdan S

2018-01-01

The increasing resistance of pathogenic bacteria to antibiotics is a challenging worldwide health problem that has led to the search for new and more efficient antibacterial agents. Nanotechnology has proven to be an effective tool for the fight against bacteria. In this paper, we present the synthesis and traits of trimetal (CuZnFe) oxide nanoparticles (NPs) using X-ray diffraction, high-resolution transmission electron microscopy, and energy dispersive x-ray spectroscopy. We evaluated the antibacterial activity of these NPs against gram-negative Escherichia coli and gram-positive Enterococcus faecalis and then compared it to that of their pure single-metal oxide components CuO and ZnO. Our study showed that the antibacterial activity of the trimetal oxide NPs was greater against E . coli than against E . faecalis . Overall, the antimicrobial effect of trimetal NPs is between those of pure ZnO and CuO nanoparticles, which may mean that their cytotoxicity is also between that of pure ZnO and CuO NPs, making them potential antibiotics. However, the cytotoxicity of trimetal NPs to mammalian cells needs to be verified. The combination of three metal oxide NPs (ZnO, CuO, and Fe 2 O 3 ) in one multimetal (CuZnFe) oxide NPs will enhance the therapeutic strategy against a wide range of microbial infections. Bacteria are unlikely to develop resistance against this new NP because bacteria must go through a series of mutations to become resistant to the trimetal oxide NP. Therefore, this NP can combat existing and emerging bacterial infections.

Nanostructured hybrid ZnO thin films for energy conversion

PubMed Central

2011-01-01

We report on hybrid films based on ZnO/organic dye prepared by electrodeposition using tetrasulfonated copper phthalocyanines (TS-CuPc) and Eosin-Y (EoY). Both the morphology and porosity of hybrid ZnO films are highly dependent on the type of dyes used in the synthesis. High photosensitivity was observed for ZnO/EoY films, while a very weak photoresponse was obtained for ZnO/TS-CuPc films. Despite a higher absorption coefficient of TS-CuPc than EoY, in ZnO/EoY hybrid films, the excited photoelectrons between the EoY levels can be extracted through ZnO, and the porosity of ZnO/EoY can also be controlled. PMID:21711909

The influence of the precursor compositional ratio on Cu2ZnSnS4 films prepared by using sulfurization of the metallic precursor

NASA Astrophysics Data System (ADS)

Amal, Muhamad I.; Kim, Kyoo Ho

2013-12-01

Cu2ZnSnS4 (CZTS) films were prepared by using the sulfurization of sputtered metallic precursors. The compositional ratio of the CZTS films was slightly different compared to their initial metallic precursors due to elemental loss during annealing. The Cu/(Zn+Sn) ratio for the CZTS-1, CZTS-2 and CZTS-3 films were 0.91, 1.06 and 1.21, respectively. In addition, all films had a compositional ratio of Zn/Sn >1. The grain sizes of the CZTS films increased with increasing Cu ratio. X-ray diffraction and Raman spectroscopy showed that the CZTS films with an excess of copper and zinc had secondary phases of Cu2SnS3 and ZnS. The optical band gap and absorption coefficient for all CZTS films in the range of the experimental compositions were calculated to be 1.5 eV and >104 cm-1, respectively. The presence of secondary phases related to compositional ratio in the CZTS films influenced the electrical properties. The CZTS-1 film with a Cu-poor and Zn-rich composition whose a carrier concentration, an electrical mobility, and a resistivity values were 2.29 × 1018 cm-3, 10.29 cm2 V-1 s-1, 3.16 Ω cm, is the most suitable for solar-cell applications.

Fast photocatalytic degradation of sulforhodamine B using ZnO:Cu nanorods

NASA Astrophysics Data System (ADS)

Raji, R.; Gopchandran, K. G.

2018-02-01

In this work, ZnO:Cu nanorods with tunable Cu content were successfully synthesized via co-precipitation method and investigations were made on the use of these nanorods as photocatalyst by observing the photodegradation of a representative dye pollutant of sulforhodamine B (SRB) under sunlight. The X-ray diffraction analysis and high resolution transmission electron microscopy showed that ZnO:Cu nanorods possess wurtzite phase with preferential growth along (101) plane. The formation of additional defect levels in these nanorods on doping with Cu and its dependence on the concentration of Cu were studied using photoluminescence and X-ray photoelectron spectroscopy. ZnO:Cu nanorods results in faster degradation of dye as compared to the undoped ZnO and is found that Cu doping enhances the photodegradation activity significantly and is highly sensitive to Cu doping level. The fast photocatalytic degradation is attributed to the fact that Cu ions promote the interfacial charge transfer and favors the effective charge separation of photogenerated electrons and holes generated during sunlight irradiation, increasing the rate of production of reactive oxygen species needed for the degradation of the dye. The chemical oxygen demand analysis of the dye solution after sunlight irradiation indicates that rate of mineralization is slower than the decoloration. The possible mechanism for degradation of dye under sunlight irradiation is described with a schematic. Additionally, the photostability of the ZnO:Cu nanorods was also tested through three repetitive cycles. This work suggest that the prepared ZnO:Cu nanorods are suitable for cost-effective water purification.

The effect of Ti-B on stabilization of Cu-Zn-Al martensite

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

Stipcich, M.; Romero, R.

1998-10-05

The application of shape memory effect in devices requires, in many cases, stable and reliable transformation temperatures. However, as a consequence of diffusional processes, in Cu-based shape memory alloys, reverse transformation temperature significantly rises after aging at temperatures above room temperature. This generally unwanted behavior is usually referred to as the stabilization of martensite. Numerous investigations have been carried out on this subject as reviewed by Ahlers and Chandrasekaran et al. Within the Cu-based alloys the Cu-Zn-Al are claimed to be more prone to stabilization than Cu-Al-Ni on aging. It has been proposed that in the Cu-Zn-Al the stabilization ismore » due to the interchange of Cu and Zn atoms assisted by vacancies, changing, consequently, the long range order inherited from the {beta} phase. In the present work, the authors investigate the stabilization behavior of polycrystalline samples of stress induced Cu-Zn-Al and Cu-Zn-Al-B martensite.« less

Preparation of high-permeability NiCuZn ferrite.

PubMed

Hu, Jun; Yan, Mi

2005-06-01

Appropriate addition of CuO/V2O5 and the reduction of the granularity of the raw materials particle decrease the sintering temperature of NiZn ferrite from 1200 degrees C to 930 degrees C. Furthermore, the magnetic properties of the NiZn ferrite prepared at low temperature of 930 degrees C is superior to that of the NiZn ferrite prepared by sintering at high temperature of 1200 degrees C because the microstructure of the NiZn ferrite sintered at 930 degrees C is more uniform and compact than that of the NiZn ferrite sintered at 1200 degrees C. The high permeability of 1700 and relative loss coefficient tandelta/mu(i) of 9.0x10(-6) at 100 kHz was achieved in the (Ni0.17Zn0.63Cu0.20)Fe1.915O4 ferrite.

Tuning the emission of aqueous Cu:ZnSe quantum dots to yellow light window

NASA Astrophysics Data System (ADS)

Wang, Chunlei; Hu, Zhiyang; Xu, Shuhong; Wang, Yanbin; Zhao, Zengxia; Wang, Zhuyuan; Cui, Yiping

2015-07-01

Synthesis of internally doped Cu:ZnSe QDs in an aqueous solution still suffers from narrow tunable emissions from the blue to green light window. In this work, we extended the emission window of aqueous Cu:ZnSe QDs to the yellow light window. Our results show that high solution pH, multiple injections of Zn precursors, and nucleation doping strategy are three key factors for preparing yellow emitted Cu:ZnSe QDs. All these factors can depress the reactivity of CuSe nuclei and Zn monomers, promoting ZnSe growth outside CuSe nuclei rather than form ZnSe nuclei separately. With increased ZnSe QD size, the conduction band and nearby trap state energy levels shift to higher energy sites, causing Cu:ZnSe QDs to have a much longer emission.

Investigation of the 68Zn(p, 2p) 67Cu nuclear reaction: New measurements up to 40 MeV and compilation up to 100 MeV

NASA Astrophysics Data System (ADS)

Szelecsényi, F.; Steyn, G. F.; Dolley, S. G.; Kovács, Z.; Vermeulen, C.; van der Walt, T. N.

2009-06-01

The excitation function was measured for the 68Zn(p, 2p) 67Cu nuclear reaction from its threshold energy up to 40 MeV. Nine pieces of highly enriched 68Zn (>98%) metal foils were irradiated to obtain reliable cross-sections using the usual stacked-foil technique. All foils were subjected to high efficiency radiochemical separation before the activity measurements. A critical compilation of the available experimental cross-section results was also performed. Thick target yields of 67Cu and the longer-lived copper radio-contaminants ( 61Cu and 64Cu) were calculated using the reliable literature results up to 100 MeV. Additionally, EOB (End Of Bombardment) contamination levels as a function of bombarding energy and irradiation time were deduced.

Preparation of high-permeability NiCuZn ferrite*

PubMed Central

Hu, Jun; Yan, Mi

2005-01-01

Appropriate addition of CuO/V2O5 and the reduction of the granularity of the raw materials particle decrease the sintering temperature of NiZn ferrite from 1200 °C to 930 °C. Furthermore, the magnetic properties of the NiZn ferrite prepared at low temperature of 930 °C is superior to that of the NiZn ferrite prepared by sintering at high temperature of 1200 °C because the microstructure of the NiZn ferrite sintered at 930 °C is more uniform and compact than that of the NiZn ferrite sintered at 1200 °C. The high permeability of 1700 and relative loss coefficient tanδ/μi of 9.0×10−6 at 100 kHz was achieved in the (Ni0.17Zn0.63Cu0.20)Fe1.915O4 ferrite. PMID:15909348

[Interaction among the trace elements zinc, copper and iron after depletion and repletion of dairy cows with zinc].

PubMed

Kirchgessner, M; Schwarz, F J; Roth, H P; Schwarz, W A

1978-12-01

Imbalances in the supply with trace elements may be caused by the excessive administration of one or several elements or the insufficient administration in relation to other trace elements. This article deals with the interactions between the trace elements zinc and copper resp. zinc and iron under the conditions of the insufficient supply with Zn (6 mg per kg dry matter of the fodder) and the supply according to the demand with other trace elements (14 mg copper resp. 83 mg iron per dry matter of the fodder). For this purpose we investigated the copper, iron and zinc content of the milk and the serum of cows that were first depleted of zinc through a semi-synthetic zinc deficiency diet and then repleted with extra allowances of zinc. The closest connections exist between the copper and zinc content of the milk. Thus extreme Zn-deficiency feeding conditions the decreased Zn-content on the one hand and increased Cu-content on the other. In contrast to this, the cows' Zn-excretion in the milk increases after Zn-repletion whereas the Cu-content decreases. This shows a distinctly negative correlation. A loose connection could only be detected for the Cu- and Zn-content of the serum. Though the Zn-content changed considerably in dependence on the Zn-supply, the Cu-content remained largely uninfluenced. The Fe-content of both milk and serum shows no interaction with the nutritive Zn-supply. Only after 19 test weeks of extreme Zn-deficiency could a slight increase of the Fe-concentration be indicated.

The effect of Cu/Zn molar ratio on CO{sub 2} hydrogenation over Cu/ZnO/ZrO{sub 2}/Al{sub 2}O{sub 3} catalyst

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

Shaharun, Salina, E-mail: salinashaharun@gmail.com, E-mail: maizats@petronas.com.my; Shaharun, Maizatul S., E-mail: salinashaharun@gmail.com, E-mail: maizats@petronas.com.my; Taha, Mohd F., E-mail: faisalt@petronas.com.my

2014-10-24

Catalytic hydrogenation of carbon dioxide (CO{sub 2}) to methanol is an attractive way to recycle and utilize CO{sub 2}. A series of Cu/ZnO/Al{sub 2}O{sub 3}/ZrO{sub 2} catalysts (CZAZ) containing different molar ratios of Cu/Zn were prepared by the co-precipitation method and investigated in a stirred slurry autoclave system. The catalysts were characterized by temperature-programmed reduction (TPR), field emission scanning electron microscopy-energy dispersive analysis (FESEM-EDX), X-ray diffraction (XRD) and N{sub 2} adsorption-desorption. Higher surface area, SA{sub BET} values (42.6–59.9 m{sup 2}/g) are recorded at low (1) and high (5) Cu/Zn ratios with the minimum value of 35.71 m{sup 2}/g found formore » a Cu/Zn of 3. The reducibility of the metal oxides formed after calcination of catalyst samples was also affected due to change in metal-support interaction. At a low reaction temperature of 443 K, total gas pressure of 3.0 MPa and 0.1 g/mL of the CZAZ catalyst, the selectivity to methanol decreased as the Cu/Zn molar ratio increased, and the maximum selectivity of 67.73 was achieved at Cu/Zn molar ratio of 1. With a reaction time of 3h, the best performing catalyst was CZAZ75 with Cu/Zn molar ratio of 5 giving methanol yield of 79.30%.« less

Production of 64Cu and 67Cu radiopharmaceuticals using zinc target irradiated with accelerator neutrons

NASA Astrophysics Data System (ADS)

Kawabata, Masako; Hashimoto, Kazuyuki; Saeki, Hideya; Sato, Nozomi; Motoishi, Shoji; Nagai, Yasuki

2014-09-01

Copper radioisotopes have gained a lot of attention in radiopharmaceuticals owing to their unique decay characteristics. The longest half-life β emitter, 67Cu, is thought to be suitable for targeted radio-immunotherapy. Adequate production of 67Cu to meet the demands of clinical studies has not been fully established. Another attractive copper isotope, 64Cu has possible applications as a diagnostic imaging tracer combined with a therapeutic effect. This work proposes a production method using accelerator neutrons in which two copper radioisotopes can be produced: 1) 68Zn(n,x)67Cu and 2) 64Zn(n,p)64Cu using ~14 MeV neutrons generated by natC(d, n) reaction, both from natural or enriched zinc oxides. The generated 64,67Cu were separated from the target zinc oxide using a chelating and an anion exchange columns and were labelled with two widely studied chelators where the labelling efficiency was found to be acceptably good. The major advantage of this method is that a significant amount of 64,67Cu with a very few impurity radionuclides are produced which also makes the separation procedure simple. Provided an accelerator supplying an Ed = ~ 40 MeV, a wide application of 64,67Cu based drugs in nuclear medicine is feasible in the near future. We will present the characteristics of this production method using accelerator neutrons including the chemical separation processes.

DENSITY FUNCTIONAL STUDY OF ELEMENTAL MERCURY ADSORPTION ON X (X=Mn, Si, Ti, Al, AND Zn)-DOPED CuO (110) SURFACE

NASA Astrophysics Data System (ADS)

He, Ping; Peng, Xiaolong; Zhang, Zhongzhi; Wu, Jiang; Chen, Naichao; Ren, Jianxing

Copper oxide (CuO) is proved to be a potential adsorbent for elemental mercury in the flue gas emitted from coal-fired power plant. However, the O-terminated CuO(110) surface has relatively week adsorption capacity for Hg. In this work, the doped method is applied to enhance the mercury adsorption capacity of O-terminated CuO(110). Mn, Si, Ti, Al and Zn are selected as the doped atom. It is found that only Zn-doped CuO (110) surfaces have the higher adsorption energy than the pure O-terminated CuO(110) surface. The mercury adsorption capacity is a complex issue, which depends on a combination of oxygen and doped element. The results suggest that the lower electropositive doped element is favorable for the improvement of mercury adsorption capacity. However, the lower electronegativity of oxygen atoms does not facilitate the mercury capture, which is different from the organic material. Cu and doped metal element, rather than oxygen atom, mainly determine mercury adsorption capacity of O-terminated CuO(110) surface, which leads to the lower adsorption capacity of the O-terminated CuO(110) surface than the Cu-terminated CuO(110) surface. The conclusions can also offer a valuable reference for the other metal oxide regarding mercury capture.

Combined copper/zinc attachment to prion protein

NASA Astrophysics Data System (ADS)

Hodak, Miroslav; Bernholc, Jerry

2013-03-01

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

Development of Useful Biomaterial for Bone Tissue Engineering by Incorporating Nano-Copper-Zinc Alloy (nCuZn) in Chitosan/Gelatin/Nano-Hydroxyapatite (Ch/G/nHAp) Scaffold.

PubMed

Forero, Juan Carlos; Roa, Eduardo; Reyes, Juan G; Acevedo, Cristian; Osses, Nelson

2017-10-17

Ceramic and metallic nanoparticles can improve the mechanical and biological properties of polymeric scaffolds for bone tissue engineering (BTE). In this work, nanohydroxyapatite (nHAp) and nano-copper-zinc alloy (nCuZn) were added to a chitosan/gelatin (Ch/G) scaffold in order to investigate the effects on morphological, physical, and biocompatibility properties. Scaffolds were fabricated by a freeze-drying technique using different pre-freezing temperatures. Microstructure and morphology were studied by scanning electron microscopy (SEM), glass transition ( T g ) was studied using differential scanning calorimetry (DSC), cell growth was estimated by MTT assay, and biocompatibility was examined in vitro and in vivo by histochemistry analyses. Scaffolds and nanocomposite scaffolds presented interconnected pores, high porosity, and pore size appropriate for BTE. T g of Ch/G scaffolds was diminished by nanoparticle inclusion. Mouse embryonic fibroblasts (MEFs) cells loaded in the Ch/G/nHAp/nCuZn nanocomposite scaffold showed suitable behavior, based on cell adhesion, cell growth, alkaline phosphatase (ALP) activity as a marker of osteogenic differentiation, and histological in vitro cross sections. In vivo subcutaneous implant showed granulation tissue formation and new tissue infiltration into the scaffold. The favorable microstructure, coupled with the ability to integrate nanoparticles into the scaffold by freeze-drying technique and the biocompatibility, indicates the potential of this new material for applications in BTE.

Effect of samarium in corrosion and microstructure of Al-5Zn-0.5Cu as low driving voltage sacrificial anode

NASA Astrophysics Data System (ADS)

Pratesa, Yudha; Ferdian, Deni; Ramadhan, Fajar Yusya; Maulana, Bramuda

2018-05-01

Sacrificial Anode Low voltage is the latest generation of the sacrificial anode that can prevent the occurrence of Hydrogen Cracking (HIC) due to overprotection. The Al-5n-0.5Cu alloy showed the potential to be developed as the new sacrificial anode. However, the main problem is copper made Al2Cu intermetallic in grain boundary. Samarium is added to modify the shape of the intermetallic to make it finer and make the corrosion uniform. Several characterizations were conducted to analyze the effect of Samarium. Scanning electron microscope (SEM) and Energy dispersive spectroscopy was used to analyzed the microstructure of the alloy. Metallography preparation was prepared for SEM analysis. Corrosion behavior was characterized by cyclic polarization in 3.5% NaCl solution. The results show samarium can change the shape of intermetallic and refine the grains. In addition, samarium makes better pitting resistance and exhibits a tendency for uniform corrosion. It is indicated by the loop reduction (ΔEpit-prot). Current density increased as an effect of samarium addition from 6x10-5 Ampere (Al-5Zn-0.5Cu) to 2.5x10-4 Ampere (Al-5Zn-0.5Cu-0.5Sm). Steel potential protection increased after addition of samarium which is an indication the possibility of Al-Zn-Cu-Sm to be used as low voltage sacrificial anode.

Interplay of Cu and oxygen vacancy in optical transitions and screening of excitons in ZnO:Cu films

NASA Astrophysics Data System (ADS)

Darma, Yudi; Seng Herng, Tun; Marlina, Resti; Fauziah, Resti; Ding, Jun; Rusydi, Andrivo

2014-02-01

We study room temperature optics and electronic structures of ZnO:Cu films as a function of Cu concentration using a combination of spectroscopic ellipsometry, photoluminescence, and ultraviolet-visible absorption spectroscopy. Mid-gap optical states, interband transitions, and excitons are observed and distinguishable. We argue that the mid-gap states are originated from interactions of Cu and oxygen vacancy (Vo). They are located below conduction band (Zn4s) and above valence band (O2p) promoting strong green emission and narrowing optical band gap. Excitonic states are screened and its intensities decrease upon Cu doping. Our results show the importance of Cu and Vo driving the electronic structures and optical transitions in ZnO:Cu films.

Simultaneous increase in strength and ductility by decreasing interface energy between Zn and Al phases in cast Al-Zn-Cu alloy.

PubMed

Han, Seung Zeon; Choi, Eun-Ae; Park, Hyun Woong; Lim, Sung Hwan; Lee, Jehyun; Ahn, Jee Hyuk; Hwang, Nong-Moon; Kim, Kwangho

2017-09-22

Cast-Al alloys that include a high amount of the second element in their matrix have comparatively high strength but low ductility because of the high volume fraction of strengthening phases or undesirable inclusions. Al-Zn alloys that have more than 30 wt% Zn have a tensile strength below 300 MPa, with elongation under 5% in the as-cast state. However, we found that after substitution of 2% Zn by Cu, the tensile strength of as-cast Al-Zn-Cu alloys was 25% higher and ductility was four times higher than for the corresponding Al-35% Zn alloy. Additionally, for the Al-43% Zn alloy with 2% Cu after 1 h solution treatment at 400 °C and water quenching, the tensile strength unexpectedly reached values close to 600 MPa. For the Al-33% Zn alloy with 2% Cu, the tensile strength was 500 MPa with 8% ductility. The unusual trends of the mechanical properties of Al-Zn alloys with Cu addition observed during processing from casting to the subsequent solution treatment were attributed to the precipitation of Zn in the Al matrix. The interface energy between the Zn particles and the Al matrix decreased when using a solution of Cu in Zn.

Serum copper and zinc concentrations in a representative sample of the Canarian population.

PubMed

Díaz Romero, Carlos; Henríquez Sánchez, Patricia; López Blanco, Félix; Rodríguez Rodríguez, Elena; Serra Majem, Lluis

2002-01-01

Serum copper (Cu) and zinc (Zn) concentrations of 395 individuals (187 males + 208 females) living in Canary Islands were determined by flame atomic absorption spectrometry. The mean copper and zinc concentrations were 1.10 +/- 0.25 mg/L and 1.16 +/- 0.52 mg/L respectively. Our data were similar to other data published in other Spanish regions. Individuals from Lanzarote presented a mean Cu and Zn concentrations higher (p < 0.05) than individuals from the rest of islands; Individuals from EL Hierro showed the lowest (p < 0.05) mean Zn concentration. These differences could be attributed a differences in Cu and Zn contents of soil and/or differences in dietary habits of the populations. The mean serum Cu concentration in females was higher (p < 0.05) than in males, however serum Zn concentration did not vary with the sex of the subjects. No relation to socio-economic status and educational level were found with respect to the serum Cu and Zn concentrations. The serum Cu concentration varied with age of individuals, observing the highest (p < 0.05) Cu concentration in the 20-30 year old interval. A higher serum Cu concentration in females within 20-30 year old interval was observed. This could be due to a higher use of oral contraceptives or to the higher number of pregnancies. Boys (younger than 15) showed a decrease (p < 0.05) of the serum Cu concentration with age. The mean Zn concentrations in serum did not change (p > 0.05) among the different age intervals. No clear trends in the serum Cu and Zn concentrations were observed when drinking and smoking habits were considered. The increase of physical exercise reduced (p < 0.05) the serum Cu concentrations.

Copper/zinc and copper/selenium ratios, and oxidative stress as biochemical markers in recurrent aphthous stomatitis.

PubMed

Ozturk, Perihan; Belge Kurutas, Ergul; Ataseven, Arzu

2013-10-01

Recurrent aphthous stomatitis (RAS) is a common oral mucosal disorder characterized by recurrent, painful oral aphthae, and oxidative stress presumably contributes to its pathogenesis. The aim of this study is to scrutinize the relationship between oxidative stress and serum trace elements (copper, Cu; zinc, Zn; selenium, Se), and to evaluate the ratios of Cu/Zn and Cu/Se in this disorder. Patients with RAS (n = 33) and age- and sex-matched healthy control subjects (n = 30) were enrolled in this study. Malondialdehyde (MDA) concentrations in plasma and the activities of superoxide dismutase (SOD1; CuZnSOD), glutathione peroxidase (GPx) and catalase (CAT) in erythrocyte were determined as spectrophotometric. Also, the levels of Se, Zn and Cu in serum were determined on flame and furnace atomic absorption spectrophotometer using Zeeman background correction. Oxidative stress was confirmed by the significant elevation in plasma MDA, and by the significant decrease in CAT, SOD1, and GPx (p < 0.05). When compared to controls, Zn and Se levels were significantly lower in patients, whereas Cu levels was higher in RAS patients than those in controls (p < 0.05). In addition, the correlation results of this study were firstly shown that there were significant and positive correlations between Se-CAT, Se-GPx, and Cu-MDA parameters, but negative correlations between Se-Cu, Se-MDA, Cu-CAT, Cu-SOD1 and Cu-GPx parameters in RAS patients. Furthermore, the ratios of Cu/Zn and Cu/Se were significantly higher in the patients than the control subjects (p < 0.05). Our results indicated that lipid peroxidation associated with the imbalance of the trace elements seems to play a crucial role in the pathogenesis of RAS. Furthermore, the serum Cu/Zn and Cu/Se ratios may be used as biochemical markers in these patients. Crown Copyright © 2013. Published by Elsevier GmbH. All rights reserved.

Pulse electro-deposition of copper on molybdenum for Cu(In,Ga)Se2 and Cu2ZnSnSe4 solar cell applications

NASA Astrophysics Data System (ADS)

Bi, Jinlian; Yao, Liyong; Ao, Jianping; Gao, Shoushuai; Sun, Guozhong; He, Qing; Zhou, Zhiqiang; Sun, Yun; Zhang, Yi

2016-09-01

The issues of rough surface morphology and the incorporated additives of the electro-deposited Cu layers, which exists in electrodeposition-based processes, is one of the major obstacles to improve the efficiency of Cu(In,Ga)Se2 (CIGSe) and Cu2ZnSnSe4 (CZTSe) solar cells. In this study, the pulse current electro-deposition method is employed to deposit smooth Cu film on Mo substrate in CuSO4 solution without any additives. Grain size of the deposited Cu film is decreased by high cathode polarization successfully. And the concentration polarization, which results from high pulse current density, is controlled successfully by adjusting the pulse frequency. Flat Cu film with smooth surface and compact structure is deposited as pulse current density @ 62.5 mA cm-2, pulse frequency @100,000 Hz, and duty cycle @ 25%. CIGSe and CZTSe absorber films with flat surface and uniform elemental distribution are prepared by selenizing the stacking metal layers electro-deposited by pulse current method. Finally, the CIGSe and CZTSe solar cells with conversion efficiency of 10.39% and 7.83% respectively are fabricated based on the smooth Cu films, which are better than the solar cells fabricated by the rough Cu film deposited by direct current electro-deposition method.

Major factors influencing bacterial leaching of heavy metals (Cu and Zn) from anaerobic sludge.

PubMed

Couillard, D; Chartier, M; Mercier, G

1994-01-01

Anaerobically digested sewage sludges were treated for heavy metal removal through a biological solubilization process called bacterial leaching (bioleaching). The solubilization of copper and zinc from these sludges is described in this study: using continuously stirred tank reactors with and without sludge recycling at different mean hydraulic residence times (1, 2, 3 and 4 days). Significant linear equations were established for the solubilization of zinc and copper according to relevant parameters: oxygen reduction potential (ORP), pH and residence time (t). Zinc solubilization was related to the residence time with a r2 (explained variance) of 0.82. Considering only t=2 and 3 days explained variance of 0.31 and 0.24 were found between zinc solubilization as a function of ORP and pH indicating a minor importance of those two factors for this metal in the range of pH and ORP experimented. Cu solubilization was weakly correlated to mean hydraulic residence time (r2=0.48), while it was highly correlated to ORP (r2=0.80) and pH (r2=0.62) considering only t of 2 and 3 days in the case of pH and ORP. The ORP dependence of Cu solubilization has been clearly demonstrated in this study. In addition to this, the importance of the substrate concentration for Cu solubilization has been confirmed. The hypothesis of a biological solubilization of Cu by the indirect mechanism has been supported. The results permit, under optimum conditions, the drawing of linear equations which will allow prediction of metal solubilization efficiencies from the parameters pH (Cu), ORP (Cu) and residence time (Cu and Zn), during the treatment. The linear regressions will be a useful tool for routine operation of the process.

Effects of enhanced zinc and copper in drinking water on spatial memory and fear conditioning

USGS Publications Warehouse

Chrosniak, L.D.; Smith, L.N.; McDonald, C.G.; Jones, B.F.; Flinn, J.M.

2006-01-01

Ingestion of enhanced zinc can cause memory impairments and copper deficiencies. This study examined the effect of zinc supplementation, with and without copper, on two types of memory. Rats raised pre- and post-natally on 10 mg/kg ZnCO3 or ZnSO4 in the drinking water were tested in a fear-conditioning experiment at 11 months of age. Both zinc groups showed a maladaptive retention of fearful memories compared to controls raised on tap water. Rats raised on 10 mg/kg ZnCO3, 10 mg/kg ZnCO3 + 0.25 mg/kg CuCl2, or tap water, were tested for spatial memory ability at 3 months of age. Significant improvements in performance were found in the ZnCO3 + CuCl2 group compared to the ZnCO3 group, suggesting that some of the cognitive deficits associated with zinc supplementation may be remediated by addition of copper. ?? 2005 Elsevier B.V. All rights reserved.

Influence of CuO and ZnO addition on the multicomponent phosphate glasses: Spectroscopic studies

NASA Astrophysics Data System (ADS)

Szumera, Magdalena; Wacławska, Irena; Sułowska, Justyna

2016-06-01

The spectra of phosphate-silicate glasses from the P2O5-SiO2-K2O-MgO-CaO system modified with the addition of CuO or ZnO have been studied by means of FTIR, Raman and 31P MAS NMR spectroscopy. All glasses were synthesized by the conventional melt-quenching technique and their homogeneous chemical composition was controlled and confirmed. By using the aforementioned research techniques, the presence of structural units with various degrees of polymerization was shown in the structure of analyzed phosphate-silicate glasses: Q3, Q2, Q1 and Q0. It was found that an increase in the content of CuO or ZnO in the composition of analyzed glasses, which are introduced at the expense of decreasing amounts of CaO and MgO, has a different influence on the phospho-oxygen network. It was shown that copper ions cause its gradual polymerization, while zinc ions cause its depolymerization. At the same time, polymerization of the silico-oxygen subnetwork was found. Additionally, in the case of glasses containing increasing amounts of ZnO, a change of the role of zinc ions in the vitreous matrix was confirmed (from the modifier to a structure-forming component).

Contrasting the material chemistry of Cu 2ZnSnSe 4 and Cu 2ZnSnS (4-x)Se x

DOE PAGES

Aguiar, Jeffery A.; Patel, Maulik; Aoki, Toshihiro; ...

2016-02-02

Earth-abundant sustainable inorganic thin-film solar cells, independent of precious elements, pivot on a marginal material phase space targeting specific compounds. Advanced materials characterization efforts are necessary to expose the roles of microstructure, chemistry, and interfaces. Here, the earth-abundant solar cell device, Cu 2ZnSnS (4-x)Se x, is reported, which shows a high abundance of secondary phases compared to similarly grown Cu 2ZnSnSe 4.

Variation in copper and zinc tolerance and accumulation in 12 willow clones: implications for phytoextraction*

PubMed Central

Yang, Wei-dong; Wang, Yu-yan; Zhao, Feng-liang; Ding, Zhe-li; Zhang, Xin-cheng; Zhu, Zhi-qiang; Yang, Xiao-e

2014-01-01

Willows (Salix spp.) have shown high potential for the phytoextraction of heavy metals. This study compares variations in copper (Cu) and zinc (Zn) tolerance and accumulation potential among 12 willow clones grown in a nutrient solution treated with 50 μmol/L of Cu or Zn, respectively. The results showed differences in the tolerance and accumulation of Cu and Zn with respect to different species/clones. The biomass variation among clones in response to Cu or Zn exposure ranged from the stimulation of growth to inhibition, and all of the clones tested showed higher tolerance to Cu than to Zn. The clones exhibited less variation in Cu accumulation but larger variation in Zn accumulation. Based on translocation factors, it was found that most of the Cu was retained in the roots and that Zn was more mobile than Cu for all clones. It is concluded that most willow clones are good accumulators of Zn and Cu. PMID:25183033

Optical and electrical properties of copper-incorporated ZnS films applicable as solar cell absorbers

NASA Astrophysics Data System (ADS)

Mehrabian, M.; Esteki, Z.; Shokrvash, H.; Kavei, G.

2016-10-01

Un-doped and Cu-doped ZnS (ZnS:Cu) thin films were synthesized by Successive Ion Layer Absorption and Reaction (SILAR) method. The UV-visible absorption studies have been used to calculate the band gap values of the fabricated ZnS:Cu thin films. It was observed that by increasing the concentration of Cu2+ ions, the Fermi level moves toward the edge of the valence band of ZnS. Photoluminescence spectra of un-doped and Cu-doped ZnS thin films was recorded under 355 nm. The emission spectrum of samples has a blue emission band at 436 nm. The peak positions of the luminescence showed a red shift as the Cu2+ ion concentration was increased, which indicates that the acceptor level (of Cu2+) is getting close to the valence band of ZnS.

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

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

NASA Astrophysics Data System (ADS)

Phoohinkong, Weerachon; Foophow, Tita; Pecharapa, Wisanu

2017-09-01

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

Effect of Copper and Silicon on Al-5%Zn Alloy as a Candidate Low Voltage Sacrificial Anode

NASA Astrophysics Data System (ADS)

Pratesa, Yudha; Ferdian, Deni; Togina, Inez

2017-05-01

One common method used for corrosion protection is a sacrificial anode. Sacrificial anodes that usually employed in the marine environment are an aluminum alloy sacrificial anode, especially Al-Zn-In. However, the electronegativity of these alloys can cause corrosion overprotection and stress cracking (SCC) on a high-strength steel. Therefore, there is a development of the sacrificial anode aluminum low voltage to reduce the risk of overprotection. The addition of alloying elements such as Cu, Si, and Ge will minimize the possibility of overprotection. This study was conducted to analyze the effect of silicon and copper addition in Al-5Zn. The experiment started from casting the sacrificial anode aluminum uses electrical resistance furnace in a graphite crucible in 800°C. The results alloy was analyzed using Optical emission spectroscopy (OES), Differential scanning calorimetry, electrochemical impedance spectroscopy, and metallography. Aluminum alloy with the addition of a copper alloy is the most suitable and efficient to serve as a low-voltage sacrificial anode aluminum. Charge transfer resistivity of copper is smaller than silicon which indicates that the charge transfer between the metal and the electrolyte is easier t to occur. Also, the current potential values in coupling with steel are also in the criteria range of low-voltage aluminum sacrificial anodes.

Chelation of Cu(II), Zn(II), and Fe(II) by tannin constituents of selected edible nuts.

PubMed

Karamać, Magdalena

2009-12-22

The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II) and Zn(II) was determined by the reaction with tetramethylmurexide, whereas for Fe(II), ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II). The Fe(II) complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II) by approximately 90%. The capacity to chelate Zn(II) was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II), whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II) chelation took place at the levels tested.

Chelation of Cu(II), Zn(II), and Fe(II) by Tannin Constituents of Selected Edible Nuts

PubMed Central

Karamać, Magdalena

2009-01-01

The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II) and Zn(II) was determined by the reaction with tetramethylmurexide, whereas for Fe(II), ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II). The Fe(II) complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II) by ~90%. The capacity to chelate Zn(II) was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II), whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II) chelation took place at the levels tested. PMID:20054482

The Effect of Different Levels of Cu, Zn and Mn Nanoparticles in Hen Turkey Diet on the Activity of Aminopeptidases.

PubMed

Jóźwik, Artur; Marchewka, Joanna; Strzałkowska, Nina; Horbańczuk, Jarosław Olav; Szumacher-Strabel, Małgorzata; Cieślak, Adam; Lipińska-Palka, Paulina; Józefiak, Damian; Kamińska, Agnieszka; Atanasov, Atanas G

2018-05-11

The aim of the study was to estimate the influence of the different levels of Cu, Zn, and Mn nanoparticles on the activity of aminopeptidases in turkey. An experiment was carried out on 144 turkey hen Hybrid Converter. The birds were divided into groups given standard- and nanoparticle-supplementation of different level of copper (Cu 20, 10, 2 mg/kg), zinc (Zn 100, 50, 10 ppm), and manganese (Mn 100, 50, 10 ppm), covering respectively 100%, 50%, and 10% of the physiological demands for those minerals in the diet. The activity of aminopeptidases (alanyl: AlaAP, leucyl: LeuAP and arginyl: ArgAP) after supplementation of minerals was determined in the breast and thigh turkey muscle. The strongest effect of interaction among minerals supplementation form and dose on the activity levels of the aminopeptidases in thigh muscle was observed for nano-Cu already at the lowest dose of 2 mg/kg. In this dose (covering 10% of the birds’ demand) nano form of supplementation significantly increased the activity of Ala-, Leu-, and ArgAP (877, 201, and 719, respectively), compared to standard form of supplementation (461, 90.5, and 576, respectively). In turn, in breast muscle, after supplementation covering 10% of the demand with the nano-Cu, nano-Zn, and nano-Mn compared to the standard form, we did not observe any significant difference in the activity levels of any of the investigated aminopeptidases, except for AlaAP under Zn supplementation. Supplementation with the 20 mg/kg of Nano-Cu (100% of demand) and with 10 mg/kg of Nano-Cu (50% of demand) inhibited the activity of all of the three aminopeptidases in thigh muscle. Supplementation of the minerals in nano form into the diet, especially of Cu and Zn in the dose covering 10% of the demand is relevant to maintain homeostasis in turkey muscles, as indicated by the activity of the aminopeptidases.

Chemical fractionation of Cu and Zn in stormwater, roadway dust and stormwater pond sediments

USGS Publications Warehouse

Camponelli, Kimberly M.; Lev, Steven M.; Snodgrass, Joel W.; Landa, Edward R.; Casey, Ryan E.

2010-01-01

This study evaluated the chemical fractionation of Cu and Zn from source to deposition in a stormwater system. Cu and Zn concentrations and chemical fractionation were determined for roadway dust, roadway runoff and pond sediments. Stormwater Cu and Zn concentrations were used to generate cumulative frequency distributions to characterize potential exposure to pond-dwelling organisms. Dissolved stormwater Zn exceeded USEPA acute and chronic water quality criteria in approximately 20% of storm samples and 20% of the storm duration sampled. Dissolved Cu exceeded the previously published chronic criterion in 75% of storm samples and duration and exceeded the acute criterion in 45% of samples and duration. The majority of sediment Cu (92–98%) occurred in the most recalcitrant phase, suggesting low bioavailability; Zn was substantially more available (39–62% recalcitrant). Most sediment concentrations for Cu and Zn exceeded published threshold effect concentrations and Zn often exceeded probable effect concentrations in surface sediments.

The effect of stoichiometry on Cu-Zn ordering kinetics in Cu2ZnSnS4 thin films

NASA Astrophysics Data System (ADS)

Rudisch, Katharina; Davydova, Alexandra; Platzer-Björkman, Charlotte; Scragg, Jonathan

2018-04-01

Cu-Zn disorder in Cu2ZnSnS4 (CZTS) may be responsible for the large open circuit voltage deficit in CZTS based solar cells. In this study, it was investigated how composition-dependent defect complexes influence the order-disorder transition. A combinatorial CZTS thin film sample was produced with a cation composition gradient across the sample area. The graded sample was exposed to various temperature treatments and the degree of order was analyzed with resonant Raman spectroscopy for various compositions ranging from E- and A-type to B-, F-, and C-type CZTS. We observe that the composition has no influence on the critical temperature of the order-disorder transition, but strongly affects the activation energy. Reduced activation energy is achieved with compositions with Cu/Sn > 2 or Cu/Sn < 1.8 suggesting an acceleration of the cation ordering in the presence of vacancies or interstitials. This is rationalized with reference to the effect of point defects on exchange mechanisms. The implications for reducing disorder in CZTS thin films are discussed in light of the new findings.

Non-blinking (Zn)CuInS/ZnS Quantum Dots Prepared by In Situ Interfacial Alloying Approach

PubMed Central

Zhang, Aidi; Dong, Chaoqing; Li, Liang; Yin, Jinjin; Liu, Heng; Huang, Xiangyi; Ren, Jicun

2015-01-01

Semiconductor quantum dots (QDs) are very important optical nanomaterials with a wide range of potential applications. However, blinking behavior of single QD is an intrinsic drawback for some biological and photoelectric applications based on single-particle emission. Herein we present a rational strategy for fabrication of non-blinking (Zn)CuInS/ZnS QDs in organic phase through in situ interfacial alloying approach. This new strategy includes three steps: synthesis of CuInS QDs, eliminating the interior traps of QDs by forming graded (Zn)CuInS alloyed QDs, modifying the surface traps of QDs by introducing ZnS shells onto (Zn)CuInS QDs using alkylthiols as sulfur source and surface ligands. The suppressed blinking mechanism was mainly attributed to modifying QDs traps from interior to exterior via a step-by-step modification. Non-blinking QDs show high quantum yield, symmetric emission spectra and excellent crystallinity, and will enable applications from biology to optoelectronics that were previously hindered by blinking behavior of traditional QDs. PMID:26458511

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

PubMed

Hill, Bruce C; Andrews, Diann

2012-06-01

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

Isolation and characterization of Cu/Zn-superoxide dismutase in Fasciola gigantica.

PubMed

Lalrinkima, H; Raina, O K; Chandra, Dinesh; Jacob, Siju Susan; Bauri, R K; Chandra, Subhash; Yadav, H S; Singh, M N; Rialch, A; Varghese, A; Banerjee, P S; Kaur, Navneet; Sharma, Arvind

2015-01-01

A full-length complementary DNA (cDNA) encoding Cu/Zn-superoxide dismutase was isolated from Fasciola gigantica that on nucleotide sequencing showed a close homology (98.9%) with Cu/Zn-superoxide dismutase (SOD) of the temperate liver fluke, F. hepatica. Expression of the gene was found in all the three developmental stages of the parasite viz. adult, newly excysted juvenile and metacercaria at transcriptional level by reverse transcription-polymerase chain reaction (RT-PCR) and at the protein level by Western blotting. F. gigantica Cu/Zn-SOD cDNA was cloned and expressed in Escherichia coli. Enzyme activity of the recombinant protein was determined by nitroblue tetrazolium (NBT)-polyacrylamide gel electrophoresis (PAGE) and this activity was inactivated by hydrogen peroxide but not by sodium azide, indicating that the recombinant protein is Cu/Zn-SOD. The enzyme activity was relatively stable at a broad pH range of pH 4.0-10.0. Native Cu/Zn-superoxide dismutase protein was detected in the somatic extract and excretory-secretory products of the adult F. gigantica by Western blotting. NBT-PAGE showed a single Cu/Zn-SOD present in the somatic extract while three SODs are released ex vivo by the adult parasite. The recombinant superoxide dismutase did not react with the serum from buffaloes infected with F. gigantica. The role of this enzyme in defense by the parasite against the host reactive oxygen species is discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu(-)(cytidine) and Cu(-)(uridine).

PubMed

Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H; Guevara-García, Alfredo; Martínez, Ana

2011-02-07

The copper-nucleoside anions, Cu(-)(cytidine) and Cu(-)(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu(-)(cytidine) and Cu(-)(uridine), respectively. According to our calculations, Cu(-)(cytidine) and Cu(-)(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu(-)(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu-(cytidine) and Cu-(uridine)

NASA Astrophysics Data System (ADS)

Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H.; Guevara-García, Alfredo; Martínez, Ana

2011-02-01

The copper-nucleoside anions, Cu-(cytidine) and Cu-(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu-(cytidine) and Cu-(uridine), respectively. According to our calculations, Cu-(cytidine) and Cu-(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu-(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

NASA Astrophysics Data System (ADS)

Wang, Kejia; Shin, Byungha; Reuter, Kathleen B.; Todorov, Teodor; Mitzi, David B.; Guha, Supratik

2011-01-01

We have carried out detailed microstructural studies of phase separation and grain boundary composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4 into ZnS and a Cu-Sn-S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such interfacial compound formation and grain boundary chemistry likely contributes to the lower than expected open circuit voltages observed for the Cu2ZnSnS4 devices.

Effects of CuZnAl Particles on Properties and Microstructure of Sn-58Bi Solder

PubMed Central

Yang, Fan; Zhang, Liang; Liu, Zhi-quan; Zhong, Su Juan; Ma, Jia; Bao, Li

2017-01-01

With the purpose of improving the properties of the Sn-58Bi lead-free solder, micro-CuZnAl particles ranging from 0 to 0.4 wt % were added into the low temperature eutectic Sn-58Bi lead-free solder. After the experimental testing of micro-CuZnAl particles on the properties and microstructure of the Sn-58Bi solders, it was found that the wettability of the Sn-58Bi solders was obviously improved with addition of CuZnAl particles. When the addition of CuZnAl particles was 0.2 wt %, the wettability of the Sn-58Bi solder performed best. At the same time, excessive addition of CuZnAl particles led to poor wettability. However, the results showed that CuZnAl particles changed the melting point of the Sn-58Bi solder slightly. The microstructure of the Sn-58Bi solder was refined by adding CuZnAl particles. When the content of CuZnAl addition was between 0.1 and 0.2 wt %, the refinement was great. In addition, the interfacial IMC layer between new composite solder and Cu substrate was thinner than that between the Sn-58Bi solder and Cu substrate. PMID:28772917

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.

Combined EXAFS and DFT Structure Calculations Provide Structural Insights into the 1:1 Multi-Histidine Complexes of CuII, CuI and ZnII with the Tandem Octarepeats of the Mammalian Prion Protein

PubMed Central

Pushie, M. Jake; Nienaber, Kurt H.; McDonald, Alex; Millhauser, Glenn L.; George, Graham N.

2014-01-01

The metal coordinating properties of the prion protein (PrP) have been the subject of intense focus and debate since the first reports of copper interaction with PrP just before the turn of the century. The picture of metal coordination to PrP has been improved and refined over the past decade, and yet the structural details of the various metal coordination modes have not been fully elucidated in some cases. Herein we employ X-ray absorption near edge spectroscopy as well as extended X-ray absorption fine structure (EXAFS) spectroscopy to structurally characterize the dominant 1:1 coordination modes for CuII, CuI and ZnII with an N-terminal fragment of PrP. The PrP fragment constitutes four tandem repeats representative of the mammalian octarepeat domain, designated OR4, which is also the most studied PrP fragment for metal interactions, making our findings applicable to a large body of previous work. Density functional theory (DFT) calculations provide additional structural and thermodynamic data, and candidate structures are used to inform EXAFS data analysis. The optimized geometries from DFT calculations are used to identify potential coordination complexes for multi-histidine coordination of CuII, CuI and ZnII in an aqueous medium, modeled using 4-methylimidazole to represent the histidine side chain. Through a combination of in silico coordination chemistry as well as rigorous EXAFS curve fitting, using full multiple scattering on candidate structures from DFT calculations, we have characterized the predominant coordination modes for the 1:1 complexes of CuII, CuI and ZnII with the OR4 peptide at pH 7.4 at atomic resolution, which are best represented as a square planar [CuII(His)4]2+, digonal [CuI(His)2]+ and tetrahedral [ZnII(His)3(OH2)]2+, respectively. PMID:25042361

Transparent Cu4O3/ZnO heterojunction photoelectric devices

NASA Astrophysics Data System (ADS)

Kim, Hong-Sik; Yadav, Pankaj; Patel, Malkeshkumar; Kim, Joondong; Pandey, Kavita; Lim, Donggun; Jeong, Chaehwan

2017-12-01

The present article reports the development of flexible, self-biased, broadband, high speed and transparent heterojunction photodiode, which is essentially important for the next generation electronic devices. We grow semitransparent p-type Cu4O3 using the reactive sputtering method at room temperature. The structural and optical properties of the Cu4O3 film were investigated by using the X-ray diffraction and UV-visible spectroscopy, respectively. The p-Cu4O3/n-ZnO heterojunction diode under dark condition yields rectification behavior with an extremely low saturation current value of 1.8 × 10-10 A and a zero bias photocurrent under illumination condition. The transparent p-Cu4O3/n-ZnO heterojunction photodetector can be operated without an external bias, due to the light-induced voltage production. The metal oxide heterojunction based on Cu4O3/ZnO would provide a route for the transparent and flexible photoelectric devices, including photodetectors and photovoltaics.

Self-Assembled Formation of Well-Aligned Cu-Te Nano-Rods on Heavily Cu-Doped ZnTe Thin Films

NASA Astrophysics Data System (ADS)

Liang, Jing; Cheng, Man Kit; Lai, Ying Hoi; Wei, Guanglu; Yang, Sean Derman; Wang, Gan; Ho, Sut Kam; Tam, Kam Weng; Sou, Iam Keong

2016-11-01

Cu doping of ZnTe, which is an important semiconductor for various optoelectronic applications, has been successfully achieved previously by several techniques. However, besides its electrical transport characteristics, other physical and chemical properties of heavily Cu-doped ZnTe have not been reported. We found an interesting self-assembled formation of crystalline well-aligned Cu-Te nano-rods near the surface of heavily Cu-doped ZnTe thin films grown via the molecular beam epitaxy technique. A phenomenological growth model is presented based on the observed crystallographic morphology and measured chemical composition of the nano-rods using various imaging and chemical analysis techniques. When substitutional doping reaches its limit, the extra Cu atoms favor an up-migration toward the surface, leading to a one-dimensional surface modulation and formation of Cu-Te nano-rods, which explain unusual observations on the reflection high energy electron diffraction patterns and apparent resistivity of these thin films. This study provides an insight into some unexpected chemical reactions involved in the heavily Cu-doped ZnTe thin films, which may be applied to other material systems that contain a dopant having strong reactivity with the host matrix.

Determination of Serum Trace Elements (Zn, Cu, and Fe) in Pakistani Patients with Rheumatoid Arthritis.

PubMed

Ullah, Zia; Ullah, Muhammad Ikram; Hussain, Shabbir; Kaul, Haiba; Lone, Khalid P

2017-01-01

Rheumatoid arthritis (RA) is a chronic autoimmune inflammatory disease, which mainly involves the joints. RA is prevalent worldwide with increasing prevalence in elderly people. The mechanism of RA pathogenesis is still undefined, and it is interplaying between genetic susceptibility and environmental factors. Although risk factors for RA are not fully established, various studies have focused on the role of trace elements in association with RA. Trace elements act as co-factors for most of the enzymes, and their deficiency is associated with many untoward effects on human health. The homeostatic alterations in the metabolism of trace elements may partly be due to inflammatory response in RA. The objective of the present study was to determine the serum concentrations and correlation of zinc, copper, and iron in RA patients and healthy controls. The study comprised of 61 RA patients and 61 age- and sex-related healthy individuals of Pakistani population. Serum levels of Zn, Cu, and Fe were measured in all the participants by atomic absorption spectrophotometer. Serum Zn and Fe were significantly reduced in the RA patients than those in the healthy controls. Serum Cu concentrations were found elevated in the RA patients. Correlation studies of trace elements determine that there was negative correlation between Zn and Cu in the RA patients and no correlation in the control group. It is very important to explore the deficiency of essential trace metals in biological samples of the RA patients in different populations which may be helpful for diagnosis and supplementary management of rheumatoid arthritis patients.

μSR investigation of a new diluted magnetic semiconductor Li(Zn,Mn,Cu)As with Mn and Cu codoping at the same Zn sites

NASA Astrophysics Data System (ADS)

Guo, S. L.; Zhao, Y.; Man, H. Y.; Ding, C.; Gong, X.; Zhi, G. X.; Fu, L. C.; Gu, Y. L.; Frandsen, B. A.; Liu, L.; Cheung, S. C.; Munsie, T. J.; Wilson, M. N.; Cai, Y. P.; Luke, G. M.; Uemura, Y. J.; Ning, F. L.

2016-09-01

We report the successful synthesis and characterization of a new type I-II-V bulk form diluted magnetic semiconductor (DMS) Li(Zn,Mn,Cu)As, in which charge and spin doping are decoupled via (Cu,Zn) and (Mn,Zn) substitution at the same Zn sites. Ferromagnetic transition temperature up to  ˜33 K has been observed with a coercive field  ˜40 Oe for the 12.5% doping level. μSR measurements confirmed that the magnetic volume fraction reaches nearly 100% at 2 K, and the mechanism responsible for the ferromagnetic interaction in this system is the same as other bulk form DMSs.

Differential Metal Tolerance and Accumulation Patterns of Cd, Cu, Pb and Zn in the Liverwort Marchantia polymorpha L.

PubMed

Ares, Ángela; Itouga, Misao; Kato, Yukari; Sakakibara, Hitoshi

2018-03-01

In this study, we investigated the bioaccumulation, tissue distribution and physiological responses to different metal concentration (0.2 and 2 mM) and time of exposure of 1, 2 and 3 weeks with cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) using the model liverwort Marchantia polymorpha. Our data showed, on one hand, a significant enrichment and tissue translocation of Cu, Zn, and specially Cd, reaching concentrations of 1800 µg g - 1 in 3 weeks. On the other hand, Pb exhibited the lowest concentration values (50 µg g - 1 ), and 90% of the total concentration in the rhizoids. We could observe a positive correlation between tissue concentration, metal translocation and an enhanced toxic response. The results obtained in this study might contribute not only in the application of this species in environmental studies with heavy metals but also as a starting point to study the evolution of metal tolerance in land plants.

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

Heavy metal (Cu, Zn, Cd and Pb) partitioning and bioaccessibility in uncontaminated and long-term contaminated soils.

PubMed

Lamb, Dane T; Ming, Hui; Megharaj, Mallavarapu; Naidu, Ravi

2009-11-15

We investigated the pore-water content and speciation of copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb) in a range of uncontaminated and long-term contaminated soils in order to establish their potential bioaccessibility to soil biota, plants and humans. Among the samples, soil pH (0.01 M CaCl(2)) ranged from 4.9 to 8.2. The total metal content of the uncontaminated soils ranged from 3.8 to 93.8 mg Cu kg(-1), 10.3 to 95 mg kg(-1) Zn, 0.1 to 1.8 mg Cd kg(-1) and 5.2 to 183 mg kg(-1) Pb, while metal content in the contaminated soils ranged from 104 to 6841 mg Cu kg(-1), 312 to 39,000 mg kg(-1) Zn, 6 to 302 mg Cd kg(-1) and 609 to 12,000 mg kg(-1) Pb. Our analysis of pore-water found the Cu concentrations to be much higher in contaminated soils than in uncontaminated soils, with the distribution coefficients (K(d)) correlating significantly with the log of dissolved organic carbon concentrations. Despite the high total metal content of the contaminated soil, Zn, Cd and Pb were not generally found at elevated levels in the pore-water with the exception of a single contaminated soil. A long period of ageing and soil weathering may have led to a substantial reduction in heavy metal concentrations in the pore-water of contaminated soils. On the other hand, Pb bioaccessibility was found to be comparatively high in Pb contaminated soils, where it tended to exceed the total Pb values by more than 80%. We conclude that, despite the extensive ageing of some contaminated soils, the bioaccessibility of Pb remains relatively high.

Nucleoside-2',3'/3',5'-bis(thio)phosphate antioxidants are also capable of disassembly of amyloid beta42-Zn(ii)/Cu(ii) aggregates via Zn(ii)/Cu(ii)-chelation.

PubMed

Hevroni, Bosmat Levi; Major, Dan Thomas; Dixit, Mudit; Mhashal, Anil Ranu; Das, Susanta; Fischer, Bilha

2016-05-18

Currently, there is an urgent need for biocompatible metal-ion chelators capable of antioxidant activity and disassembly of amyloid beta (Aβ)-aggregates as potential therapeutics for Alzheimer's disease (AD). We recently demonstrated the promising antioxidant activity of adenine/guanine 2',3' or 3',5'-bis(thio)phosphate analogues, 2'-dA/G3'5'PO/S and A2'3'PO/S, and their affinity to Zn(ii)-ions. These findings encouraged us to evaluate them as agents for the dissolution of Aβ42-Zn(ii)/Cu(ii) aggregates. Specifically, we explored their ability to bind Cu(ii)/Zn(ii)-ions, the geometry and stoichiometry of these complexes, Cu(ii)/Zn(ii)-binding-sites and binding mode, and the ability of these analogues to dissolve Aβ42-Zn(ii)/Cu(ii) aggregates, as well as their effect on the secondary structure of those aggregates. Finally, we identified the most promising agents for dissolution of Aβ42-Zn(ii)/Cu(ii) aggregates. Specifically, we observed the formation of a 1 : 1 complex between 2'-dG3'5'PO and Cu(ii), involving O4 ligands. Zn(ii) was coordinated by both thiophosphate groups of 2'-dA3'5'PS and A2'3'PS involving O2S2 ligands in a 1 : 1 stoichiometry. A2'3'PS dissolves Aβ42-Zn(ii) and Aβ42-Cu(ii) aggregates as effectively as, and 2.5-fold more effectively than EDTA, respectively. Furthermore, 2'-dG3'5'PS and A2'3'PS reverted the Aβ42-M(ii) structure, back to that of the free Aβ42. Finally, cryo-TEM and TEM images confirmed the disassembly of Aβ42 and Aβ42-M(ii) aggregates by A2'3'PS. Hence, 2'-dG3'5'PS and A2'3'PS may serve as promising scaffolds for new AD therapeutics, acting as both effective antioxidants and agents for solubilization of Aβ42-Cu(ii)/Zn(ii) aggregates.

Use of PIXE to measure serum copper, zinc, selenium, and bromine in patients with hematologic malignancies

NASA Astrophysics Data System (ADS)

Beguin, Y.; Bours, V.; Delbrouck, J.-M.; Robaye, G.; Roelandts, I.; Fillet, G.; Weber, G.

1990-04-01

The use of PIXE allowed for a simultaneous determination of serum copper (Cu), zinc (Zn), selenium (Se) and bromine (Br), in various groups of patients with hematologic malignancies. In 78 patients with acute nonlymphocytic leukemia, it was observed that (1) serum Se was significantly lower than in healthy controls and correlated inversely with the tumor burden; (2) serum bromine was normal at diagnosis but dropped dramatically after intensive chemotherapy, before recovering progressively over a period of months; and (3) pretreatment serum copper and zinc were significant prognostic factors of the chance to achieve a complete remission. In 50 patients with chronic lymphocytic leukemia, it was observed that (1) serum Cu and Cu/Zn ratio were useful indices of the disease activity, which were independent of a nonspecific acute phase reaction; and (2) Zn deficiency could contribute to immune dysfunction. In 119 patients with myeloproliferative disorders or myelodysplasic syndromes, serum Cu and Zn levels were mostly dependent on nonspecific factors, such as age and inflammation.

Fabrication and applications of copper sulfide (CuS) nanostructures

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

Shamraiz, Umair, E-mail: umairshamraiz@gmail.com; Hussain, Raja Azadar, E-mail: hussainazadar@gamil.com; Badshah, Amin, E-mail: aminbadshah@yahoo.com

2016-06-15

This review article presents different fabrication procedures (under the headlines of solvothermal routes, aerosol methods, solution methods and thermolysis), and applications (photocatalytic degradation, ablation of cancer cells, electrode material in lithium ion batteries and in gas sensing, organic solar cells, field emission properties, super capacitor applications, photoelectrochemical performance of QDSCs, photocatalytic reduction of organic pollutants, electrochemical bio sensing, enhanced PEC characteristics of pre-annealed CuS film electrodes) of copper sulfide (Covellite). - Highlights: • This review article presents the synthesis and applications of copper sulfide. • CuS has been used over the years for different applications in nanoscience. • Different syntheticmore » protocols are followed for their preparation which help in the possible modifications in the morphology of CuS.« less

Electrochemical performance of CuNCN for sodium ion batteries and comparison with ZnNCN and lithium ion batteries

NASA Astrophysics Data System (ADS)

Eguia-Barrio, A.; Castillo-Martínez, E.; Klein, F.; Pinedo, R.; Lezama, L.; Janek, J.; Adelhelm, P.; Rojo, T.

2017-11-01

Transition metal carbodiimides (TMNCN) undergo conversion reactions during electrochemical cycling in lithium and sodium ion batteries. Micron sized copper and zinc carbodiimide powders have been prepared as single phase as confirmed by PXRD and IR and their thermal stability has been studied in air and nitrogen atmosphere. CuNCN decomposes at ∼250 °C into CuO or Cu while ZnNCN can be stable until 400 °C and 800 °C in air and nitrogen respectively. Both carbodiimides were electrochemically analysed for sodium and lithium ion batteries. The electrochemical Na+ insertion in CuNCN exhibits a relatively high reversible capacity (300 mAh·g-1) which still indicates an incomplete conversion reaction. This incomplete reaction confirmed by ex-situ EPR analysis, is partly due to kinetic limitations as evidenced in the rate capability experiments and in the constant potential measurements. On the other hand, ZnNCN shows incomplete conversion reaction but with good capacity retention and lower hysteresis as negative electrode for sodium ion batteries. The electrochemical performance of these materials is comparable to that of other materials which operate through displacement reactions and is surprisingly better in sodium ion batteries in comparison with lithium ion batteries.

Facile Route to Rare Heterobimetallic Aluminum-Copper and Aluminum-Zinc Selenide Clusters.

PubMed

Li, Bin; Li, Jiancheng; Liu, Rui; Zhu, Hongping; Roesky, Herbert W

2017-03-20

Heterobimetallic aluminum-copper and aluminum-zinc clusters were prepared from the reaction of LAl(SeH) 2 [1; L = HC(CMeNAr) 2 and Ar = 2,6-iPr 2 C 6 H 3 ] with (MesCu) 4 and ZnEt 2 , respectively. The resulting clusters with the core structures of Al 2 Se 4 Cu 4 and Al 2 Se 4 Zn 3 exhibit unique metal-organic frameworks. This is a novel pathway for the synthesis of aluminum-copper and aluminum-zinc selenides. The products have been characterized by spectroscopic methods and single-crystal X-ray structural characterization.

Microstructures and Mechanical Properties of Cu and Cu-Zn Alloys

NASA Astrophysics Data System (ADS)

Ma, Xiaolong

Strength and ductility are two crucial mechanical properties of structural materials, which, unfortunately, are often mutually exclusive based on the conventional design of microstructures and their deformation physics. This is also true in most nanostructured (NS) metals and alloys although they exhibit record-high strength. However, the disappointingly inadequate ductility becomes the major roadblock to their practical utilities due to the threat of catastrophic failure in load-bearing applications. Therefore, simultaneous improvement of strength and ductility or a well-defined trade-off between these two properties, i.e. increasing either of them without significant loss of the other, in NS materials has garnered extensive efforts from the research community. A few strategies have been explored to handle this long-standing challenge with promise. In this dissertation work, two of those strategies, deformation twins and laminate/gradient structures are specified with particular interests in NS Cu and Cu-Zn alloys. The author believes the observation and the revealed underlying mechanism are fundamental and therefore shed lights on their universal application to other metallic material systems. Deformation twins have been frequently observed in ultra-fined grained (UFG) and NS face-centered cubic (FCC) metals and alloys, which is closely related to the better strengthening and strain hardening in mechanical performance. Previous findings even show that there exist an optimum grain size range within nano scale, where the deformation twins are of most frequency, i.e. most stable in pure FCC metals. However, such grain-size dependent twinning phenomenon is still unclear in FCC alloys. We report, for the first time in systematic experiments, the observed optimum grain sizes for deformation twins in NS Cu-Zn alloys slightly increase with increasing Zn content. Our results indicate that alloying changes the relationship between the stacking-fault and twin-fault energy

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.

Functional Performances of CuZnAl Shape Memory Alloy Open-Cell Foams

NASA Astrophysics Data System (ADS)

Biffi, C. A.; Casati, R.; Bassani, P.; Tuissi, A.

2018-01-01

Shape memory alloys (SMAs) with cellular structure offer a unique mixture of thermo-physical-mechanical properties. These characteristics can be tuned by changing the pore size and make the shape memory metallic foams very attractive for developing new devices for structural and functional applications. In this work, CuZnAl SMA foams were produced through the liquid infiltration of space holder method. In comparison, a conventional CuZn brass alloy was foamed trough the same method. Functional performances were studied on both bulk and foamed SMA specimens. Calorimetric response shows similar martensitic transformation (MT) below 0 °C. Compressive response of CuZnAl revealed that mechanical behavior is strongly affected by sample morphology and that damping capacity of metallic foam is increased above the MT temperatures. The shape memory effect was detected in the CuZnAl foams. The conventional brass shows a compressive response similar to that of the martensitic CuZnAl, in which plastic deformation accumulation occurs up to the cellular structure densification after few thermal cycles.

Distribution and mobility of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb) from ammunition residues on shooting ranges for small arms located on mires.

PubMed

Mariussen, Espen; Johnsen, Ida Vaa; Strømseng, Arnljot Einride

2017-04-01

An environmental survey was performed on shooting ranges for small arms located on minerotrophic mires. The highest mean concentrations of Pb (13 g/kg), Cu (5.2 g/kg), Zn (1.1 g/kg), and Sb (0.83 g/kg) in the top soil were from a range located on a poor minerotrophic and acidic mire. This range had also the highest concentrations of Pb, Cu, Zn, and Sb in discharge water (0.18 mg/L Pb, 0.42 mg/L Cu, 0.63 mg/L Zn, and 65 μg/L Sb) and subsurface soil water (2.5 mg/L Pb, 0.9 mg/L Cu, 1.6 mg/L Zn, and 0.15 mg/L Sb). No clear differences in the discharge of ammunition residues between the mires were observed based on the characteristics of the mires. In surface water with high pH (pH ~7), there was a trend with high concentrations of Sb and lower relative concentrations of Cu and Pb. The relatively low concentrations of ammunition residues both in the soil and soil water, 20 cm below the top soil, indicates limited vertical migration in the soil. Channels in the mires, made by plant roots or soil layer of less decomposed materials, may increase the rate of transport of contaminated surface water into deeper soil layers and ground water. A large portion of both Cu and Sb were associated to the oxidizable components in the peat, which may imply that these elements form inner-sphere complexes with organic matter. The largest portion of Pb and Zn were associated with the exchangeable and pH-sensitive components in the peat, which may imply that these elements form outer-sphere complexes with the peat.

Oxidation of nitroxyl anion to nitric oxide by copper ions

PubMed Central

Nelli, Silvia; Hillen, Mark; Buyukafsar, Kansu; Martin, William

2000-01-01

This study made use of a nitric oxide-sensitive electrode to examine possible means of generating nitric oxide from nitroxyl anion (NO−) released upon the decomposition of Angeli's salt. Our results show that copper ions (from CuSO4) catalyze the rapid and efficient oxidation of nitroxyl to nitric oxide. Indeed, the concentrations of copper required to do so (0.1–100 μM) are roughly 100-times lower than those required to generate equivalent amounts of nitric oxide from S-nitroso-N-acetyl-D,L-penicillamine (SNAP). Experiments with ascorbate (1 mM), which reduces Cu2+ ions to Cu+, and with the Cu2+ chelators, EDTA and cuprizone, and the Cu+ chelator, neocuproine, each at 1 mM, suggest that the oxidation is catalyzed by copper ions in both valency states. Some compounds containing other transition metals, i.e. methaemoglobin, ferricytochrome c and Mn(III)TMPyP, were much less efficient than CuSO4 in catalyzing the formation of nitric oxide from nitroxyl, while FeSO4, FeCl3, MnCl2, and ZnSO4 were inactive. Of the copper containing enzymes examined, Cu-Zn superoxide dismutase and ceruloplasmin were weak generators of nitric oxide from nitroxyl, even at concentrations (2500 and 30 u ml−1, respectively) vastly greater than are present endogenously. Two others, ascorbate oxidase (10 u ml−1) and tyrosinase (250 u ml−1) were inactive. Our findings suggest that a copper-containing enzyme may be responsible for the rapid oxidation of nitroxyl to nitric oxide by cells, but the identity of such an enzyme remains elusive. PMID:10991931

Facile synthesis and photocatalytic activity of bi-phase dispersible Cu-ZnO hybrid nanoparticles

NASA Astrophysics Data System (ADS)

Liu, Xiao; Liu, HongLing; Zhang, WenXing; Li, XueMei; Fang, Ning; Wang, XianHong; Wu, JunHua

2015-04-01

Bi-phase dispersible Cu-ZnO hybrid nanoparticles were synthesized by one-pot non-aqueous nanoemulsion with the use of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) show high crystallinity of the Cu-ZnO hybrid nanoparticles and an average particle size of ~19.4 nm. The ultraviolet-visible light absorbance spectrometry (UV-vis) and photoluminescence spectrophotometry (PL) demonstrate well dispersibility and excellent optical performance of Cu-ZnO hybrid nanoparticles both in organic and aqueous solvent. The X-ray photoelectron spectroscopy (XPS) confirms Cu1+ and Cu2+ in ZnO. The observation using Sudan red (III) as probe molecule reveals that the Cu-ZnO hybrid nanoparticles possess enhanced photocatalytic activity and stability which are promising for potential applications in photocatalysis.

Effect of Zn-doping on structural and magnetic properties of copper ferrite nanoparticles

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

Gautam, Nisha; Thirupathi, Gadipelly; Singh, Rajender

2016-05-23

The nanoparticles of CuFe{sub 2}O{sub 4} (CF) and Cu{sub 0.8}Zn{sub 0.2}Fe{sub 2}O{sub 4} (CZF) were synthesized using co-precipitation method to study the effect of Zn doping in Cu-ferrite. The X-ray diffraction (XRD) patterns were well fitted with two-phase structure using Rietveld analysis as Fd-3 m space group (spinel system) and C12/c1 space group (monoclinic system CuO-phase). The average crystallite size of the CF and CZF nanoparticles for spinel structure are 6 and 7 nm respectively. The spinel phase fraction is increased from 56% to 71% with Zn-doping of 20% in CF. The transmission electron micrograph analysis showed the narrow size distribution formore » CZF nanoparticles. The magnetization plots as a function of magnetic field (M (H)) of CF and CZF nanoparticles indicate superparamagnetic behavior. The magnetization is increased with Zn-doping in CF. The stable spinel Cu-ferrite can be obtained with Zn-doping in CF.« less

Biocompatibility Assessment of Novel Bioresorbable Alloys Mg-Zn-Se and Mg-Zn-Cu for Endovascular Applications: In- Vitro Studies.

PubMed

Persaud-Sharma, Dharam; Budiansky, Noah; McGoron, Anthony J

2013-01-01

Previous studies have shown that using biodegradable magnesium alloys such as Mg-Zn and Mg-Zn-Al possess the appropriate mechanical properties and biocompatibility to serve in a multitude of biological applications ranging from endovascular to orthopedic and fixation devices. The objective of this study was to evaluate the biocompatibility of novel as-cast magnesium alloys Mg-1Zn-1Cu wt.% and Mg-1Zn-1Se wt.% as potential implantable biomedical materials, and compare their biologically effective properties to a binary Mg-Zn alloy. The cytotoxicity of these experimental alloys was evaluated using a tetrazolium based- MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) assay and a lactate dehydrogenase membrane integrity assay (LDH). The MTS assay was performed on extract solutions obtained from a 30-day period of alloy immersion and agitation in simulated body fluid to evaluate the major degradation products eluted from the alloy materials. Human foreskin fibroblast cell growth on the experimental magnesium alloys was evaluated for a 72 hour period, and cell death was quantified by measuring lactate dehydrogenase concentrations. Both Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. The Mg-Zn-Cu alloy was found to completely degrade within 72 hours, resulting in lower human foreskin fibroblast cell viability. The Mg-Zn-Se alloy was shown to be less cytotoxic than both the Mg-Zn-Cu and Mg-Zn alloys.

Biocompatibility Assessment of Novel Bioresorbable Alloys Mg-Zn-Se and Mg-Zn-Cu for Endovascular Applications: In- Vitro Studies

PubMed Central

Budiansky, Noah; McGoron, Anthony J.

2013-01-01

Previous studies have shown that using biodegradable magnesium alloys such as Mg-Zn and Mg-Zn-Al possess the appropriate mechanical properties and biocompatibility to serve in a multitude of biological applications ranging from endovascular to orthopedic and fixation devices. The objective of this study was to evaluate the biocompatibility of novel as-cast magnesium alloys Mg-1Zn-1Cu wt.% and Mg-1Zn-1Se wt.% as potential implantable biomedical materials, and compare their biologically effective properties to a binary Mg-Zn alloy. The cytotoxicity of these experimental alloys was evaluated using a tetrazolium based- MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) assay and a lactate dehydrogenase membrane integrity assay (LDH). The MTS assay was performed on extract solutions obtained from a 30-day period of alloy immersion and agitation in simulated body fluid to evaluate the major degradation products eluted from the alloy materials. Human foreskin fibroblast cell growth on the experimental magnesium alloys was evaluated for a 72 hour period, and cell death was quantified by measuring lactate dehydrogenase concentrations. Both Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. The Mg-Zn-Cu alloy was found to completely degrade within 72 hours, resulting in lower human foreskin fibroblast cell viability. The Mg-Zn-Se alloy was shown to be less cytotoxic than both the Mg-Zn-Cu and Mg-Zn alloys. PMID:24058329

Models for the mechanism for activating copper-zinc superoxide dismutase in the absence of the CCS Cu chaperone in Arabidopsis.

PubMed

Huang, Chien-Hsun; Kuo, Wen-Yu; Jinn, Tsung-Luo

2012-03-01

Copper-zinc superoxide dismutase (CuZnSOD; CSD) is an important antioxidant enzyme for oxidative stress protection. To date, two activation pathways have been identified in many species. One requiring the CCS, Cu chaperone for SOD, to insert Cu and activate CSD (referred to as CCS-dependent pathway), and the other works independently of CCS (referred to as CCS-independent pathway). In our previous study, we suggest an unidentified factor will work with glutathione (GSH) for CSD activation in the absence of the CCS. Here, two models of the CCS-independent mechanism are proposed. The role of the unidentified factor may work as a scaffold protein, which provides a platform for the CSD protein and Cu-GSH to interact, or as a Cu carrier, which itself can bind Cu and interact with CSD proteins. We also suggest that the CSD protein conformation at C-terminal is important in providing a docking site for unidentified factor to access.

Eu3 + amidst ionic copper in glass: Enhancement through energy transfer from Cu+, or quenching by Cu2 +?

NASA Astrophysics Data System (ADS)

Jiménez, José A.

2017-02-01

A barium-phosphate glass system doped with europium(III) and containing a high concentration of copper(I) together with a copper(II) remnant has been studied spectroscopically. The main object is to elucidate whether the orange-red emission of Eu3 + ions succeeds through sensitization via luminescent Cu+ ions or else is preferentially quenched by non-radiative transfer to Cu2 +. A characterization of the melt-quenched glass was first performed by UV/Vis optical absorption, 31P nuclear magnetic resonance and infrared absorption spectroscopy. A photoluminescence (PL) spectroscopy and emission decay dynamics assessment was subsequently performed. Despite the concentration of Cu+ being estimated to be much higher than that of Cu2 +, the data shows that quenching of Eu3 + PL by Cu2 + dominates. The lifetime analysis of emitting centers Cu+ and Eu3 + points to the origin of the manifestation being that the Eu3 + → Cu2 + non-radiative transfer rate responsible for the quenching is almost two times higher than that for the Cu+ → Eu3 + transfer accountable for the enhancement. Finally, an effort was made for the determination of Cu2 + in the glass containing Cu+, Cu2 + and Eu3 + ions based on the Eu3 + (5D0) emission decay rates. It was found to be in excellent agreement with the UV/Vis spectrophotometric approach, thus supporting the utility of Eu3 + ions for optical sensing of copper(II) in the solid state.

Cu-rGO subsurface layer creation on copper substrate and its resistance to oxidation

NASA Astrophysics Data System (ADS)

Pietrzak, Katarzyna; Strojny-Nędza, Agata; Olesińska, Wiesława; Bańkowska, Anna; Gładki, Andrzej

2017-11-01

On the basis of a specially designed experiment, this paper presents a model, which is an attempt to explain the mechanism of formatting and creating oxidation resistance of Cu-rGO subsurface layers. Practically zero chemical affinity of copper to carbon is a fundamental difficulty in creating composite structures of Cu-C, properties which are theoretically possible to estimate. In order to bind the thermally reduced graphene oxide with copper surface, the effect of structural rebuilding of the copper oxide, in the process of annealing in a nitrogen atmosphere, have been used. On intentionally oxidized and anoxic copper substrates the dispersed graphene oxide (GO) and thermally reduced graphene oxide (rGO) were loaded. Annealing processes after the binding effects of both graphene oxide forms to Cu substrates were tested. The methods for high-resolution electron microscopy were found subsurface rGO-Cu layer having a substantially greater resistance to oxidation than pure copper. The mechanism for the effective resistance to oxidation of the Cu-rGO has been presented in a hypothetical form.

Cu(I)-mediated Allosteric Switching in a Copper-sensing Operon Repressor (CsoR)*

PubMed Central

Chang, Feng-Ming James; Coyne, H. Jerome; Cubillas, Ciro; Vinuesa, Pablo; Fang, Xianyang; Ma, Zhen; Ma, Dejian; Helmann, John D.; García-de los Santos, Alejandro; Wang, Yun-Xing; Dann, Charles E.; Giedroc, David P.

2014-01-01

The copper-sensing operon repressor (CsoR) is representative of a major Cu(I)-sensing family of bacterial metalloregulatory proteins that has evolved to prevent cytoplasmic copper toxicity. It is unknown how Cu(I) binding to tetrameric CsoRs mediates transcriptional derepression of copper resistance genes. A phylogenetic analysis of 227 DUF156 protein members, including biochemically or structurally characterized CsoR/RcnR repressors, reveals that Geobacillus thermodenitrificans (Gt) CsoR characterized here is representative of CsoRs from pathogenic bacilli Listeria monocytogenes and Bacillus anthracis. The 2.56 Å structure of Cu(I)-bound Gt CsoR reveals that Cu(I) binding induces a kink in the α2-helix between two conserved copper-ligating residues and folds an N-terminal tail (residues 12–19) over the Cu(I) binding site. NMR studies of Gt CsoR reveal that this tail is flexible in the apo-state with these dynamics quenched upon Cu(I) binding. Small angle x-ray scattering experiments on an N-terminally truncated Gt CsoR (Δ2–10) reveal that the Cu(I)-bound tetramer is hydrodynamically more compact than is the apo-state. The implications of these findings for the allosteric mechanisms of other CsoR/RcnR repressors are discussed. PMID:24831014

Dilute electrodeposition of TiO2 and ZnO thin film memristors on Cu substrate

NASA Astrophysics Data System (ADS)

Fauzi, F. B.; Ani, M. H.; Herman, S. H.; Mohamed, M. A.

2018-03-01

Memristor has become one of the alternatives to replace the current memory technologies. Fabrication of titanium dioxide, TiO2 memristor has been extensively studied by using various deposition methods. However, recently more researches have been done to explore the compatibility of other transition metal oxide, TMO such as zinc oxide, ZnO to be used as the active layer of the memristor. This paper highlights the simple and easy-control electrodeposition to deposit titanium, Ti and zinc, Zn thin film at room temperature and subsequent thermal oxidation at 600 °C. Gold, Au was then sputtered as top electrode to create metal-insulator-metal, MIM sandwich of Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristors. The structural, morphological and memristive properties were characterized using Field Emission Scanning Electron Microscopy, FESEM, X-Ray Diffraction, XRD and current-voltage, I-V measurement. Both Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristivity were identified by the pinched hysteresis loop with resistive ratio of 1.2 and 1.08 respectively. Empirical study on diffusivity of Ti4+, Zn2+ and O2‑ ions in both metal oxides show that the metal vacancies were formed, thus giving rise to its memristivity. The electrodeposited Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristors demonstrate comparable performances to previous studies using other methods.

Luminescence of polyethylene glycol coated CdSeTe/ZnS and InP/ZnS nanoparticles in the presence of copper cations.

PubMed

Beaune, Grégory; Tamang, Sudarsan; Bernardin, Aude; Bayle-Guillemaud, Pascale; Fenel, Daphna; Schoehn, Guy; Vinet, Françoise; Reiss, Peter; Texier, Isabelle

2011-08-22

The use of click chemistry for quantum dot (QD) functionalization could be very promising for the development of bioconjugates dedicated to in vivo applications. Alkyne-azide ligation usually requires copper(I) catalysis. The luminescence response of CdSeTe/ZnS nanoparticles coated with polyethylene glycol (PEG) is studied in the presence of copper cations, and compared to that of InP/ZnS QDs coated with mercaptoundecanoic acid (MUA). The quenching mechanisms appear different. Luminescence quenching occurs without any wavelength shift in the absorption and emission spectra for the CdSeTe/ZnS/PEG nanocrystals. In this case, the presence of copper in the ZnS shell is evidenced by energy-filtered transmission electron microscopy (EF-TEM). By contrast, in the case of InP/ZnS/MUA nanocrystals, a redshift of the excitation and emission spectra, accompanied by an increase in absorbance and a decrease in photoluminescence, is observed. For CdSeTe/ZnS/PEG nanocrystals, PL quenching is enhanced for QDs with 1) smaller inorganic-core diameter, 2) thinner PEG shell, and 3) hydroxyl terminal groups. Whereas copper-induced PL quenching can be interesting for the design of sensitive cation sensors, copper-free click reactions should be used for the efficient functionalization of nanocrystals dedicated to bioapplications, in order to achieve highly luminescent QD bioconjugates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoluminescence spectra of thin films of ZnTPP–C{sub 60} and CuTPP–C{sub 60} molecular complexes

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

Elistratova, M. A., E-mail: marina.elistratova@mail.ioffe.ru; Zakharova, I. B.; Romanov, N. M.

2016-09-15

The results of studies of thin composite films of zinc and copper tetraphenylporphyrins with different fractions of fullerene C{sub 60} are reported. The photoluminescence spectra are recorded, and the composition and surface morphology are analyzed by means of scanning electron microscopy. The results show a difference in the structure of films with two types of metals (Zn, Cu) entering into the complex of the porphyrin macrocycle. An additional long-wavelength photoluminescence band at 1.4 eV is detected for the first time, which is evidence of the formation of ZnTPP–C{sub 60} molecular complexes from a gas-dynamic vapor flow upon condensation. In CuTPPmore » thin films, the processes of self-assembly into nanowires 20 nm in diameter and up to 50 µm in length and the formation of nanoheterojunctions upon the addition of fullerene C{sub 60} are observed. Quantum-chemical calculations in the context of density-functional theory are carried out to interpret the experimental data.« less

[Effect of heat treatment on the structure of a Cu-Zn-Al-Ni system dental alloy].

PubMed

Guastaldi, A C; Adorno, A T; Beatrice, C R; Mondelli, J; Ishikiriama, A; Lacefield, W

1990-01-01

This article characterizes the structural phases present in the copper-based metallic alloy system "Cu-Zn-Al-Ni" developed for dental use, and relates those phases to other properties. The characterization was obtained after casting (using the lost wax process), and after heat treatment. In order to obtain better corrosion resistance by changing the microstructure, the castings were submitted to 30, 45 and 60 minutes of heat treatment at the following temperatures: 750 degrees C, 800 degrees C, and 850 degrees C. The various phases were analyzed using X-ray diffraction and scanning electron microscopy (SEM). The results after heat treatment showed a phase (probably Cu3Al), that could be responsible for the improvement in the alloy's resistance to corrosion as compared to the as-cast structure.

Electrodeposition and Characterization of Mn-Cu-Zn Alloys for Corrosion Protection Coating

NASA Astrophysics Data System (ADS)

Tsurtsumia, Gigla; Gogoli, David; Koiava, Nana; Kakhniashvili, Izolda; Jokhadze, Nunu; Lezhava, Tinatin; Nioradze, Nikoloz; Tatishvili, Dimitri

2017-12-01

Mn-Cu-Zn alloys were electrodeposited from sulphate bath, containing citrate or EDTA and their mixtures as complexing ligands. The influence of bath composition and deposition parameters on alloys composition, cathodic current efficiency and structural and electrochemical properties were studied. At a higher current density (≥ 37.5 A dm-2) a uniform surface deposit of Mn-Cu-Zn was obtained. Optimal pH of electrolyte (0.3 mol/dm3Mn2+ + 0.6 mol/dm3 (NH4)2SO4 +0.1 mol/dm3Zn2++0.005 mol/dm3 Cu2++ 0.05mol/dm3Na3Cit + 0.15mol/dm3 EDTA; t=300C; τ=20 min) for silvery, nonporous coating of Mn-Cu-Zn alloy was within 6.5-7.5; coating composition: 71-83% Mn, 6-7.8% Cu, 11.5-20% Zn, current efficiency up to 40%. XRD patterns revealed BCT (body centred tetragonal) γ-Mn solid phase solution (lattice constants a=2.68 Å c=3.59 Å). Corrosion measurements of deposited alloys were performed in aerated 3.5% NaCl solution. The corrosion current density (icorr) of the electrodeposited alloys on carbon steel was 10 times lower than corrosion rate of pure zinc and manganese coatings. Triple alloy coatings corrosion potential (Ecorr = -1140 mV vs. Ag/AgCl) preserved negative potential value longer (more than three months) compared to carbon steel substrate (Ecorr = -670 mV vs. Ag/AgCl). Tafel polarization curves taken on Mn-Cu-Zn alloy coating in aerated 3.5% NaCl solution did not show a typical passivation behaviour which can be explained by formation oflow solubility of adherent corrosion products on the alloy surface. Corrosion test of Mn-Cu-Zn electrocoating in chlorine environment shows that it is the best cathodic protective coating for a steel product.

Cu,Zn superoxide dismutase: cloning and analysis of the Taenia solium gene and Taenia crassiceps cDNA.

PubMed

Parra-Unda, Ricardo; Vaca-Paniagua, Felipe; Jiménez, Lucia; Landa, Abraham

2012-01-01

Cytosolic Cu,Zn superoxide dismutase (Cu,Zn-SOD) catalyzes the dismutation of superoxide (O(2)(-)) to oxygen and hydrogen peroxide (H(2)O(2)) and plays an important role in the establishment and survival of helminthes in their hosts. In this work, we describe the Taenia solium Cu,Zn-SOD gene (TsCu,Zn-SOD) and a Taenia crassiceps (TcCu,Zn-SOD) cDNA. TsCu,Zn-SOD gene that spans 2.841 kb, and has three exons and two introns; the splicing junctions follow the GT-AG rule. Analysis in silico of the gene revealed that the 5'-flanking region has three putative TATA and CCAAT boxes, and transcription factor binding sites for NF1 and AP1. The transcription start site was a C, located at 22 nucleotides upstream of the translation start codon (ATG). Southern blot analysis showed that TcCu,Zn-SOD and TsCu,Zn-SOD genes are encoded by a single copy. The deduced amino acid sequences of TsCu,Zn-SOD gene and TcCu,Zn-SOD cDNA reveal 98.47% of identity, and the characteristic motives, including the catalytic site and β-barrel structure of the Cu,Zn-SOD. Proteomic and immunohistochemical analysis indicated that Cu,Zn-SOD does not have isoforms, is distributed throughout the bladder wall and is concentrated in the tegument of T. solium and T. crassiceps cysticerci. Expression analysis revealed that TcCu,Zn-SOD mRNA and protein expression levels do not change in cysticerci, even upon exposure to O(2)(-) (0-3.8 nmol/min) and H(2)O(2) (0-2mM), suggesting that this gene is constitutively expressed in these parasites. Published by Elsevier Inc.

A comparative study of pure and copper (Cu)-doped ZnO nanorods for antibacterial and photocatalytic applications with their mechanism of action

NASA Astrophysics Data System (ADS)

Bhuyan, Tamanna; Khanuja, Manika; Sharma, R.; Patel, S.; Reddy, M. R.; Anand, S.; Varma, A.

2015-07-01

The present study reports the synthesis of pure and Cu-doped ZnO nanorods for antibacterial and photocatalytic applications. The samples were synthesized by simple, low cost mechanical-assisted thermal decomposition process. The synthesized materials were characterized by scanning electron microscopy, UV-Visible spectroscopy, and photoluminescence studies. The antibacterial activity of characterized samples was determined against Gram-positive bacteria such as Staphylococcus aureus and Streptococcus pyogenes and Gram-negative bacteria such as Escherichia coli using shake flask method with respect to time. The significant antibacterial activity was perceived from scanning electron micrographs that clearly revealed bacterial cell lysis resulting in the release of cytoplasmic content followed by cell death. The degradation of methylene blue was used as a model organic dye for photocatalytic activity. The present study demonstrates the superior photocatalytic and antibacterial activity of Cu-doped ZnO nanorods with respect to pure ZnO nanorods.

Solar Absorber Cu 2 ZnSnS 4 and its Parent Multilayers ZnS/SnS 2 /Cu 2 S Synthesized by Atomic Layer Deposition and Analyzed by X-ray Photoelectron Spectroscopy

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

Baryshev, Sergey V.; Riha, Shannon C.; Zinovev, Alexander V.

2015-06-01

Presented here are results of x-ray photoelectron spectroscopy (XPS) on multilayers of metal-sulfide binaries ZnS, SnS2, and Cu2S grown by atomic layer deposition (ALD) on Si substrates, and of Cu2ZnSnS4 (CZTS) formed upon 450 °C annealing of the parent multilayer ZnS/SnS2/Cu2S. Survey and detailed spectral analysis of the multilayer ZnS/SnS2/Cu2S are presented step-wise, as each layer was sequentially added by ALD. The set of data is finalized with spectra of the resulting alloy CZTS. XPS analyses indicate significant mixing between SnS2 and Cu2S, which favors CZTS formation within the ALD approach.

Towards Stable CuZnAl Slurry Catalysts for the Synthesis of Ethanol from Syngas

NASA Astrophysics Data System (ADS)

Dong, Weibing; Gao, Zhihua; Zhang, Qian; Huang, Wei

2018-07-01

A stable CuZnAl slurry catalyst for the synthesis of ethanol from syngas has been developed by adjusting the heat treatment conditions of the complete liquid-phase method. The activity evaluation results showed that the CuZnAl catalyst, when heat-treated under a high pressure and temperature, was a stable catalyst for the synthesis of ethanol. The selectivity of ethanol using the CuZnAl slurry catalyst, which was heat-treated at 553 K under 4.0 MPa, increased continuously with time and was stable at approximately 26.00% after 144 h. The characterization results indicated that the CuZnAl slurry catalyst heat-treated under high pressure conditions could facilitate the formation of a more perfect structure with a larger specific surface area. The prepared catalyst contained a balance of strong and weak acid sites, an appropriate form of Cu2O and a high Cu/Zn atomic ratio at the catalyst surface, providing its stability in ethanol synthesis from syngas.

The Cu2ZnSnSe4 thin films solar cells synthesized by electrodeposition route

NASA Astrophysics Data System (ADS)

Li, Ji; Ma, Tuteng; Wei, Ming; Liu, Weifeng; Jiang, Guoshun; Zhu, Changfei

2012-06-01

An electrodeposition route for preparing Cu2ZnSnSe4 thin films for thin film solar cell absorber layers is demonstrated. The Cu2ZnSnSe4 thin films are prepared by co-electrodeposition Cu-Zn-Sn metallic precursor and subsequently annealing in element selenium atmosphere. The structure, composition and optical properties of the films were investigated by X-ray diffraction (XRD), Raman spectrometry, energy dispersive spectrometry (EDS) and UV-VIS absorption spectroscopy. The Cu2ZnSnSe4 thin film with high crystalline quality was obtained, the band gap and absorption coefficient were 1.0 eV and 10-4 cm-1, which is quite suitable for solar cells fabrication. A solar cell with the structure of ZnO:Al/i-ZnO/CdS/Cu2ZnSnSe4/Mo/glass was fabricated and achieved an conversion efficiency of 1.7%.

Effect of Cu-Dopant on the Structural, Magnetic and Electrical Properties of ZnO

NASA Astrophysics Data System (ADS)

Aryanto, D.; Kurniawan, C.; Subhan, A.; Sudiro, T.; Sebayang, P.; Ginting, M.; Siregar, S. M. K.; Nasruddin, M. N.

2017-05-01

Zn1- x Cu x O (x = 0, 2, 3, and 4 at.%) was synthesized by using solid-state reaction technique. The ZnO and CuO powders were mixed and then milled by using high-speed shaker mill. The influence of Cu dopants on the structure, magnetic, and electrical properties was investigated by using XRD, VSM, and I-V and C-V measurements. The XRD analysis showed that the Zn1- x Cu x O had hexagonal wurtzite polycrystalline. The diffraction intensity decreased and the peak position shifted directly to a higher 2θ angle with increasing the dopant concentration. Furthermore, the lattice parameters decreased when the ZnO was doped with x = 0.04, which indicated that the crystal structure changed. The increase of Cu dopants was believed to affect the magnetic and electrical properties of ZnO.

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis.

PubMed

Li, Shanshan; Zhang, Chen; Wang, Meng; Li, Yu

2014-01-01

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13%. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (-1.072 and -24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.

Hydrometallurgical Extraction of Zinc and Copper A 57Fe-Mössbauer and XRD Approach

NASA Astrophysics Data System (ADS)

Mulaba-Bafubiandi, A. F.; Waanders, F. B.

2005-02-01

The most commonly used route in the hydrometallurgical extraction of zinc and copper from a sulphide ore is the concentrate roast leach electro winning process. In the present investigation a zinc copper ore from the Maranda mine, located in the Murchison Greenstone Belt, South Africa, containing sphalerite (ZnS) and chalcopyrite (CuFeS2), was studied. The 57Fe-Mössbauer spectrum of the concentrate yielded pyrite, chalcopyrite and clinochlore, consistent with XRD data. Optimal roasting conditions were found to be 900°C for 3 h and the calcine produced contained according to X-ray diffractometry equal amounts of franklinite (ZnFe2O4) and zinc oxide (ZnO) and half the amount of willemite (Zn2SiO4). The Mössbauer spectrum showed predominantly franklinite (59%), hematite (6%) and other Zn- or Cu-depleted ferrites (35%). The latter could not be detected by XRD analyses as peak overlapping with other species occurred. Leaching was done with HCl, H2SO4 and HNO3, to determine which process would result in maximum recovery of Zn and Cu. More than 80% of both were recovered by using either one of the three techniques. From the residue of the leaching, the Fe-compounds were precipitated and <1% of the Zn and Cu was not recovered.

Electron paramagnetic resonance in Cu-doped ZnO

NASA Astrophysics Data System (ADS)

Buchheit, R.; Acosta-Humánez, F.; Almanza, O.

2016-04-01

In this work, ZnO and Cu-doped ZnO nanoparticles (Zn1-xCuxO, x = 3%), with a calcination temperature of 500∘C were synthesized using the sol-gel method. The particles were analyzed using atomic absorption spectroscopy (AAS), X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) at X-band, measurement in a temperature range from 90 K to room temperature. AAS confirmed a good correspondence between the experimental doping concentration and the theoretical value. XRD reveals the presence of ZnO phase in hexagonal wurtzite structure and a nanoparticle size for the samples synthesized. EPR spectroscopy shows the presence of point defects in both samples with g-values of g = 1.959 for shallow donors and g = 2.004 for ionized vacancies. It is important when these materials are required have been used as catalysts, as suggested that it is not necessary prepare them at higher temperature. A simulation of the Cu EPR signal using an anisotropic spin Hamiltonian was performed and showed good coincidence with the experimental spectra. It was shown that Cu2+ ions enter interstitial octahedral sites of orthorhombic symmetry in the wurtzite crystal structure. Temperature dependence of the EPR linewidth and signal intensity shows a paramagnetic behavior of the sample in the measurement range. A Néel temperature TN = 78 ± 19 K was determined.

Copper Ion from Cu2O Crystal Induces AMPK-Mediated Autophagy via Superoxide in Endothelial Cells

PubMed Central

Seo, Youngsik; Cho, Young-Sik; Huh, Young-Duk; Park, Heonyong

2016-01-01

Copper is an essential element required for a variety of functions exerted by cuproproteins. An alteration of the copper level is associated with multiple pathological conditions including chronic ischemia, atherosclerosis and cancers. Therefore, copper homeostasis, maintained by a combination of two copper ions (Cu+ and Cu2+), is critical for health. However, less is known about which of the two copper ions is more toxic or functional in endothelial cells. Cubic-shaped Cu2O and CuO crystals were prepared to test the role of the two different ions, Cu+ and Cu2+, respectively. The Cu2O crystal was found to have an effect on cell death in endothelial cells whereas CuO had no effect. The Cu2O crystals appeared to induce p62 degradation, LC3 processing and an elevation of LC3 puncta, important processes for autophagy, but had no effect on apoptosis and necrosis. Cu2O crystals promote endothelial cell death via autophagy, elevate the level of reactive oxygen species such as superoxide and nitric oxide, and subsequently activate AMP-activated protein kinase (AMPK) through superoxide rather than nitric oxide. Consistently, the AMPK inhibitor Compound C was found to inhibit Cu2O-induced AMPK activation, p62 degradation, and LC3 processing. This study provides insight on the pathophysiologic function of Cu+ ions in the vascular system, where Cu+ induces autophagy while Cu2+ has no detected effect. PMID:26743904

Interactions and Toxicity of Cu-Zn mixtures to Hordeum vulgare in Different Soils Can Be Rationalized with Bioavailability-Based Prediction Models.

PubMed

Qiu, Hao; Versieren, Liske; Rangel, Georgina Guzman; Smolders, Erik

2016-01-19

Soil contamination with copper (Cu) is often associated with zinc (Zn), and the biological response to such mixed contamination is complex. Here, we investigated Cu and Zn mixture toxicity to Hordeum vulgare in three different soils, the premise being that the observed interactions are mainly due to effects on bioavailability. The toxic effect of Cu and Zn mixtures on seedling root elongation was more than additive (i.e., synergism) in soils with high and medium cation-exchange capacity (CEC) but less than additive (antagonism) in a low-CEC soil. This was found when we expressed the dose as the conventional total soil concentration. In contrast, antagonism was found in all soils when we expressed the dose as free-ion activities in soil solution, indicating that there is metal-ion competition for binding to the plant roots. Neither a concentration addition nor an independent action model explained mixture effects, irrespective of the dose expressions. In contrast, a multimetal BLM model and a WHAM-Ftox model successfully explained the mixture effects across all soils and showed that bioavailability factors mainly explain the interactions in soils. The WHAM-Ftox model is a promising tool for the risk assessment of mixed-metal contamination in soils.

Effects on external quantum efficiency of electrochemically constructed n-ZnO/p-Cu2O photovoltaic device by annealing

NASA Astrophysics Data System (ADS)

Khoo, Pei Loon; Kikkawa, Yuuki; Shinagawa, Tsutomu; Izaki, Masanobu

2017-07-01

Cuprous oxide (Cu2O), a terrestrial abundant, low cost, nontoxic, intrinsically p-type oxide semiconductor with bandgap energy of about 2eV, has recently received increasing attention as a light absorbing layer in solar cells. However, the performances of electrochemically constructed Cu2O solar devices are poor compared to the theoretical power conversion efficiency. This research was conducted focusing on the EQE performance, which is closely related to the short circuit current of a solar device. ZnO/Cu2O-PV-devices were constructed electrochemically with 3-electrode cell on Ga:ZnO/SLG substrates; ZnO layers were deposited from an aqueous solution of 8 mmolL-1 zinc nitrate hexahydrate at 63°C, 0.01 Coulomb cm-2, and -0.8V, while Cu2O layers were deposited from aqueous solution containing 0.4 molL-1 copper (II) acetate monohydrate (pH12.5), at 40°C, 1.5 Coulomb cm-2, and -0.4V. Devices were then annealed under different temperatures of 150°C, 200°C, 250°C, and 300°C for 60 minutes with a Rapid Thermal Anneal furnace (RTA). The EQE of the devices were measured with a spectral sensitivity device and compared to the non-annealed device. Further studies were made such as morphology observation of the films by FE-SEM and measurements of X-ray diffraction patterns. Annealed samples showed improved maximum EQE at 150-200°C of annealing, indicating that EQE above 90% can be achieved, proving the validity of EQE improvement via low temperature annealing method for thin film Cu2O photovoltaic devices.

The case for metamorphic base metal mineralization: pyrite chemical, Cu and S isotope data from the Cu-Zn deposit at Kupferberg in Bavaria, Germany

NASA Astrophysics Data System (ADS)

Höhn, S.; Frimmel, H. E.; Debaille, V.; Pašava, J.; Kuulmann, L.; Debouge, W.

2017-12-01

The stratiform Cu-Zn sulfide deposit at Kupferberg in Germany represents Bavaria's largest historic base metal producer. The deposit is hosted by Early Paleozoic volcano-sedimentary strata at the margin of a high-grade allochthonous metamorphic complex. The present paper reports on the first Cu and S isotope data as well as trace element analyses of pyrite from this unusual deposit. The new data point to syn-orogenic mineralization that was driven by metamorphic fluids during nappe emplacement. Primary Cu ore occurs as texturally late chalcopyrite within stratiform laminated pyrite in black shale in two different tectonostratigraphic units of very low and low metamorphic grade, respectively, that were juxtaposed during the Variscan orogeny. Trace element contents of different pyrite types suggest the presence of at least one hydrothermal pyrite generation (mean Co/Ni = 35), with the other pyrite types being syn-sedimentary/early diagenetic (mean Co/Ni = 3.7). Copper isotope analyses yielded a narrow δ65Cu range of -0.26 to 0.36‰ for all ore types suggesting a hypogene origin for the principal chalcopyrite mineralization. The ore lenses in the two different tectonostratigraphic units differ with regard to their δ34S values, but little difference exists between poorly and strongly mineralized domains within a given locality. A genetic model is proposed in which syn-sedimentary/early diagenetic pyrite with subordinate chalcopyrite and sphalerite formed in black shale beds in the two different stratigraphic units, followed by late-tectonic strata-internal, hydrothermal mobilization of Fe, Cu, and Zn during syn-orogenic thrusting, which concentrated especially Cu to ore grade. In agreement with this model, Cu distribution in stream sediments in this region shows distinct enrichments bound to the margin of the allochthonous complex. Thus, Kupferberg can be considered a rare example of a syn-orogenic Cu deposit with the Cu probably being derived from syn

A facile green antisolvent approach to Cu2+-doped ZnO nanocrystals with visible-light-responsive photoactivities.

PubMed

Lu, Yi-Hsuan; Lin, Wei-Hao; Yang, Chao-Yao; Chiu, Yi-Hsuan; Pu, Ying-Chih; Lee, Min-Han; Tseng, Yuan-Chieh; Hsu, Yung-Jung

2014-08-07

An environmentally benign antisolvent method has been developed to prepare Cu(2+)-doped ZnO nanocrystals with controllable dopant concentrations. A room temperature ionic liquid, known as a deep eutectic solvent (DES), was used as the solvent to dissolve ZnO powders. Upon the introduction of the ZnO-containing DES into a bad solvent which shows no solvation to ZnO, ZnO was precipitated and grown due to the dramatic decrease of solubility. By adding Cu(2+) ions to the bad solvent, the growth of ZnO from the antisolvent process was accompanied by Cu(2+) introduction, resulting in the formation of Cu(2+)-doped ZnO nanocrystals. The as-prepared Cu(2+)-doped ZnO showed an additional absorption band in the visible range (400-800 nm), which conduced to an improvement in the overall photon harvesting efficiency. Time-resolved photoluminescence spectra, together with the photovoltage information, suggested that the doped Cu(2+) may otherwise trap photoexcited electrons during the charge transfer process, inevitably depressing the photoconversion efficiency. The photoactivity of Cu(2+)-doped ZnO nanocrystals for photoelectrochemical water oxidation was effectively enhanced in the visible region, which achieved the highest at 2.0 at% of Cu(2+). A further increase in the Cu(2+) concentration however led to a decrease in the photocatalytic performance, which was ascribed to the significant carrier trapping caused by the increased states given by excessive Cu(2+). The photocurrent action spectra illustrated that the enhanced photoactivity of the Cu(2+)-doped ZnO nanocrystals was mainly due to the improved visible photon harvesting achieved by Cu(2+) doping. These results may facilitate the use of transition metal ion-doped ZnO in other photoconversion applications, such as ZnO based dye-sensitized solar cells and magnetism-assisted photocatalytic systems.

Complete transformation of ZnO and CuO nanoparticles in culture medium and lymphocyte cells during toxicity testing.

PubMed

Ivask, Angela; Scheckel, Kirk G; Kapruwan, Pankaj; Stone, Vicki; Yin, Hong; Voelcker, Nicolas H; Lombi, Enzo

2017-03-01

Here, we present evidence on complete transformation of ZnO and CuO nanoparticles, which are among the most heavily studied metal oxide particles, during 24 h in vitro toxicological testing with human T-lymphocytes. Synchrotron radiation-based X-ray absorption near edge structure (XANES) spectroscopy results revealed that Zn speciation profiles of 30 nm and 80 nm ZnO nanoparticles, and ZnSO 4 - exposed cells were almost identical with the prevailing species being Zn-cysteine. This suggests that ZnO nanoparticles are rapidly transformed during a standard in vitro toxicological assay, and are sequestered intracellularly, analogously to soluble Zn. Complete transformation of ZnO in the test conditions was further supported by almost identical Zn spectra in medium to which ZnO nanoparticles or ZnSO 4 was added. Likewise, Cu XANES spectra for CuO and CuSO 4 -exposed cells and cell culture media were similar. These results together with our observation on similar toxicological profiles of ZnO and soluble Zn, and CuO and soluble Cu, underline the importance of dissolution and subsequent transformation of ZnO and CuO nanoparticles during toxicological testing and provide evidence that the nano-specific effect of ZnO and CuO nanoparticles is negligible in this system. We strongly suggest to account for this aspect when interpreting the toxicological results of ZnO and CuO nanoparticles.

Cu0-loaded SBA-15@ZnO with improved electrical properties and affinity towards hydrogen

NASA Astrophysics Data System (ADS)

Bouazizi, N.; Louhichi, S.; Ouargli, R.; Bargougui, R.; Vieillard, J.; Derf, F. Le; Azzouz, A.

2017-05-01

A core-shell material was prepared using SBA-15 crystallites as cores for the growth of a ZnO shell, followed by Cu0 dispersion. The resulting Cu/SBA-15@ZnO nanostructure displayed higher specific surface area (SSA) and higher number of smaller pores as compared to the starting materials. Dispersion of fine Cu0NPs induced a compaction of the host matrice and a marked decay of the hydrophilic character, explained in terms of the involvement of terminal hydroxyl groups in competitive sbnd HO:Cu interaction at the expense of H-bridges with water. Heating at 400-450 °C seems to trigger ZnO dehydroxylation with possible self-polycondensation and/or the formation of Si-O-Zn bridges. This is an additional explanation of the significant SSA increase and decrease in the average pore diameter. Both ZnO and Cu0NP incorporation induced shifts in the UV-vis absorption band towards higher wavelengths, indicating a decrease in the optical band gap energy and an improvement of the conductance properties. As compared to ZnO, Cu0NPs produced stronger improvement of the conductance, which was found to increase with higher frequencies. Cu/SBA-15@ZnO also displayed higher affinity towards hydrogen as compared to SBA-15@ZnO and SBA-15 at ambient conditions. These outstanding properties combined to an appreciable thermal stability are worth to be prone to deeper investigations, because they can open promising prospects for Cu/SBA-15@ZnO as sensor, electrode material, electrocatalyst and/or hydrogen capture matrice.

Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction

DOE PAGES

Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; ...

2016-10-17

Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level ofmore » Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.« less

Highly Luminescent Water-Dispersible NIR-Emitting Wurtzite CuInS2/ZnS Core/Shell Colloidal Quantum Dots

PubMed Central

2017-01-01

Copper indium sulfide (CIS) quantum dots (QDs) are attractive as labels for biomedical imaging, since they have large absorption coefficients across a broad spectral range, size- and composition-tunable photoluminescence from the visible to the near-infrared, and low toxicity. However, the application of NIR-emitting CIS QDs is still hindered by large size and shape dispersions and low photoluminescence quantum yields (PLQYs). In this work, we develop an efficient pathway to synthesize highly luminescent NIR-emitting wurtzite CIS/ZnS QDs, starting from template Cu2-xS nanocrystals (NCs), which are converted by topotactic partial Cu+ for In3+ exchange into CIS NCs. These NCs are subsequently used as cores for the overgrowth of ZnS shells (≤1 nm thick). The CIS/ZnS core/shell QDs exhibit PL tunability from the first to the second NIR window (750–1100 nm), with PLQYs ranging from 75% (at 820 nm) to 25% (at 1050 nm), and can be readily transferred to water upon exchange of the native ligands for mercaptoundecanoic acid. The resulting water-dispersible CIS/ZnS QDs possess good colloidal stability over at least 6 months and PLQYs ranging from 39% (at 820 nm) to 6% (at 1050 nm). These PLQYs are superior to those of commonly available water-soluble NIR-fluorophores (dyes and QDs), making the hydrophilic CIS/ZnS QDs developed in this work promising candidates for further application as NIR emitters in bioimaging. The hydrophobic CIS/ZnS QDs obtained immediately after the ZnS shelling are also attractive as fluorophores in luminescent solar concentrators. PMID:28638177

Copper to Zinc Ratio as Disease Biomarker in Neonates with Early-Onset Congenital Infections

PubMed Central

Wisniewska, Monika; Cremer, Malte; Wiehe, Lennart; Becker, Niels-Peter; Rijntjes, Eddy; Martitz, Janine; Renko, Kostja; Bührer, Christoph; Schomburg, Lutz

2017-01-01

Copper (Cu) and zinc (Zn) are essential trace elements for regular development. Acute infections alter their metabolism, while deficiencies increase infection risks. A prospective observational case-control study was conducted with infected (n = 21) and control (n = 23) term and preterm newborns. We analyzed trace element concentrations by X-ray fluorescence, and ceruloplasmin (CP) by Western blot. Median concentration of Cu at birth (day 1) was 522.8 [387.1–679.7] μg/L, and Zn was 1642.4 ± 438.1 μg/L. Cu and Zn correlated positively with gestational age in control newborns. Cu increased in infected newborns from day 1 to day 3. CP correlated positively to Cu levels at birth in both groups and on day 3 in the group of infected neonates. The Cu/Zn ratio was relatively high in infected newborns. Interleukin (IL)-6 concentrations on day 1 were unrelated to Cu, Zn, or the Cu/Zn ratio, whereas C-reactive protein (CRP) levels on day 3 correlated positively to the Cu/Zn -ratio at both day 1 and day 3. We conclude that infections affect the trace element homeostasis in newborns: serum Zn is reduced, while Cu and CP are increased. The Cu/Zn ratio combines both alterations, independent of gestational age. It may, thus, constitute a meaningful diagnostic biomarker for early-onset infections. PMID:28358335

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

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

Gao, Weidong; Cao, Di; Jin, Yunxue

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

DOE PAGES

Gao, Weidong; Cao, Di; Jin, Yunxue; ...

2018-04-18

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

Speciation of Cu and Zn in drainage water from agricultural soils.

PubMed

Aldrich, Annette P; Kistler, David; Sigg, Laura

2002-11-15

Inputs of copper and zinc from agricultural soils into the aquatic system were investigated in this study, because of their heavy agricultural usage as feed additives and components of fertilizers and fungicides. As the mobility and bioavailability of these metals are affected by their speciation, the lipophilic, colloidal and organic fractions were determined in drainage water from a loamy and a humic soil treated with fungicides or manure. This study therefore investigates the impact of agricultural activity on a natural environment and furthers our understanding of the mobility of metals in agricultural soils and aquatic pollution in rural areas. Marked increases in the total dissolved metal concentrations were observed in the drainage water during rain events with up to 0.3 microM Cu and 0.26 microM Zn depending on the intensity of the rainfall and soil type. The mobile metal fractions were of a small molecular size (<10 kD) and mainly hydrophilic. Lipophilic complexes originating from a dithiocarbamate (DTC) fungicide could not be observed in the drainage water; however, small amounts of lipophilic metal complexes may be of natural origin. Cu was organically complexed to > 99.9% by abundant organic ligands (log K 10.5-11.0). About 50% of dissolved Zn were electrochemically labile, and the other 50% were complexed by strong organic ligands (log K 8.2-8.6). Therefore very little free metal species were found suggesting a low bioavailability of these metals in the drainage water even at elevated metal concentrations.

Visible light-driven photocatalytic H{sub 2}-generation activity of CuS/ZnS composite particles

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

Xiao, Liang; Chen, Hua; Huang, Jianhua, E-mail: jhhuang@zstu.edu.cn

2015-04-15

Highlights: • Preparation of CuS/ZnS composite photocatalyst by cation-exchange reaction. • Visible light photocatalytic activity for H{sub 2} evolution without cocatalyst. • The H{sub 2}-evolution rate from water splitting depends on the CuS content. • The highest rate of H{sub 2} evolution is obtained with CuS (0.5 mol%)/ZnS composite. - Abstract: CuS/ZnS composite particles with diameter of 200–400 nm were successfully prepared by a simple cation-exchange reaction using ZnS spheres as a precursor. CuS nanoparticles with a few nanometers in diameter were observed on the surface of composite particles. The synthesized CuS/ZnS composite particles showed photocatalytic property effective for H{submore » 2} evolution from an aqueous Na{sub 2}S and Na{sub 2}SO{sub 3} solution under visible light irradiation without any cocatalysts. The rate of H{sub 2} generation was found to be strongly dependent on the CuS content. The highest rate of H{sub 2} evolution reached 695.7 μmol h{sup −1} g{sup −1}, which was almost 7 times as high as that of the mechanical mixture of CuS and ZnS. The enhancement in the photocatalytic activity of CuS/ZnS composite particles is supposed to be due to the direct interfacial charge transfer of the CuS/ZnS heterojunction.« less

ZnO/Cu nanocomposite: a platform for direct electrochemistry of enzymes and biosensing applications.

PubMed

Yang, Chi; Xu, Chunxiang; Wang, Xuemei

2012-03-06

Unique structured nanomaterials can facilitate the direct electron transfer between redox proteins and the electrodes. Here, in situ directed growth on an electrode of a ZnO/Cu nanocomposite was prepared by a simple corrosion approach, which enables robust mechanical adhesion and electrical contact between the nanostructured ZnO and the electrodes. This is great help to realize the direct electron transfer between the electrode surface and the redox protein. SEM images demonstrate that the morphology of the ZnO/Cu nanocomposite has a large specific surface area, which is favorable to immobilize the biomolecules and construct biosensors. Using glucose oxidase (GOx) as a model, this ZnO/Cu nanocomposite is employed for immobilization of GOx and the construction of the glucose biosensor. Direct electron transfer of GOx is achieved at ZnO/Cu nanocomposite with a high heterogeneous electron transfer rate constant of 0.67 ± 0.06 s(-1). Such ZnO/Cu nanocomposite provides a good matrix for direct electrochemistry of enzymes and mediator-free enzymatic biosensors.

Synthesis of ZnO/CuO and TiO{sub 2}/CuO nanocomposites for light and ultrasound assisted degradation of a textile dye in aqueous solution

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

Muzakki, Afifah; Shabrany, Hesni; Saleh, Rosari, E-mail: rosari.saleh@gmail.com, E-mail: rosari.saleh@ui.ac.id

2016-04-19

ZnO/CuO and TiO2/CuO nanocomposites with different Zn/Cu and Ti/Cu ratios were prepared using sol-gel method. The obtained composite samples were used as catalyst. Methylene blue was used as a model of textile dye to evaluate their photocatalytic, sonocatalytic and photosonocatalytic activities. X-ray diffraction and energy dispersive X- ray analysis confirmed that only monoclinic CuO and hexagonal wurtzite ZnO structures are present in ZnO/CuO nanocomposites, while in TiO2/CuO nanocomposites monoclinic CuO and anatase TiO2 structures were observed. The degradation of methylene blue indicated that the incorporation of CuO in ZnO/CuO and TiO2/CuO nanocomposites exhibited an appreciable higher photocatalytic activity, which wasmore » mainly attributed to the extended photoresponding range and more light energy could be utilized than pure ZnO and TiO2.« less

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

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during

Improved ohmic contact of Ga-Doped ZnO to p-GaN by using copper sulfide intermediate layers

NASA Astrophysics Data System (ADS)

Gu, Wen; Xu, Tao; Zhang, Jianhua

2013-11-01

Copper sulfide (CuS) was used as the intermediate layer to build ohmic contact of Ga-Doped ZnO (GZO) transparent conduction layer (TCL) to p-GaN. The CuS and GZO layers were prepared by thermal evaporation and RF magnetron sputtering, respectively. Although the GZO-only contacts to p-GaN exhibit nonlinear behavior, ohmic contact with a specific contact resistance of 1.6 × 10-2 Ω cm2 has been realized by inserting 3 nm CuS layer between GZO and p-GaN. The optical transmittance of CuS/GZO film was measured to be higher than 80% in the range of 450-600 nm wavelength. The possible mechanism for the ohmic contact behavior can be attributed to the increased hole concentration of p-GaN surface induced by CuS films after annealing. The forward voltage of LEDs with CuS/GZO TCL has been reduced by 1.7 V at 20 mA and the output power has been increased by 29.6% at 100 mA compared with LEDs without CuS interlayer. These results indicated that using CuS intermediate layer could be a potential ohmic contact method to realize high-efficiency LEDs.

Effects of annealing on the ferromagnetism and photoluminescence of Cu-doped ZnO nanowires.

PubMed

Xu, H J; Zhu, H C; Shan, X D; Liu, Y X; Gao, J Y; Zhang, X Z; Zhang, J M; Wang, P W; Hou, Y M; Yu, D P

2010-01-13

Room temperature ferromagnetic Cu-doped ZnO nanowires have been synthesized using the chemical vapor deposition method. By combining structural characterizations and comparative annealing experiments, it has been found that both extrinsic (CuO nanoparticles) and intrinsic (Zn(1-x)Cu(x)O nanowires) sources are responsible for the observed ferromagnetic ordering of the as-grown samples. As regards the former, annealing in Zn vapor led to a dramatic decrease of the ferromagnetism. For the latter, a reversible switching of the ferromagnetism was observed with sequential annealings in Zn vapor and oxygen ambience respectively, which agreed well with previous reports for Cu-doped ZnO films. In addition, we have for the first time observed low temperature photoluminescence changed with magnetic properties upon annealing in different conditions, which revealed the crucial role played by interstitial zinc in directly mediating high T(c) ferromagnetism and indirectly modulating the Cu-related structured green emission via different charge transfer transitions.

Fate and forms of Cu in a reservoir ecosystem following copper sulfate treatment (Saint Germain les Belles, France)

NASA Astrophysics Data System (ADS)

van Hullebusch, E.; Chatenet, P.; Deluchat, V.; Chazal, P. M.; Froissard, D.; Lens, P. N. L.; Baudu, M.

2003-05-01

Copper sulfate (CuSO4) addition to freshwater for phytoplankton control has been practiced for decades, and remains the most effective algicidal treatment for numerous managed water bodies. A reservoir in the centre of France was the site for an investigation of copper distribution in aquatic systems after a copper sulfate treatment Results of copper monitoring showed a rapid conversion of dissolved Cu to particulate forms, with significant accumulation in the sediments/83% of total copper added). Total sediment Cu content increasedfrom approximately 37.7 to 45.4 μg.g^{-1} dry weight after the first treatment. Sequential extraction suggested that a significanl portion of the sediment-borne Cu was associated with the organic fraction which may release Cu to the water column, although significant release would occur only under extreme changes in water chemistry. Based upon measured Cu concentrations, flows at the down-stream water, and known mass applied during treatment, mass balance calculations indicated that approximately 17% of the Cu was exported from the reservoir over a 70 day period following a 196 μg.L^{-l} Cu^{2+} (as CuSO4, 5 H2O) treatment. The largest amount of copper was probably adsorbed on downstream sediment or lost in running water, Copper bioaccumulation by a moss, Fontinalis antipyretica, in the down-stream water showed that it was possible to distinguish between a treated and an untreated area. The impact of copper treatment in the down-stream reservoir could be followed using mosses. The bioaccumulation data further showed that there is a distance effect which could be exploited to determine potential copper impact on receiving water bodies. Thirty days after copper sulfate addition, Fontinalis still indicated copper exposure.

Growth of Cu2ZnSnSe4 Film under Controllable Se Vapor Composition and Impact of Low Cu Content on Solar Cell Efficiency.

PubMed

Li, Jianjun; Wang, Hongxia; Wu, Li; Chen, Cheng; Zhou, Zhiqiang; Liu, Fangfang; Sun, Yun; Han, Junbo; Zhang, Yi

2016-04-27

It is a challenge to fabricate high quality Cu2ZnSnSe4 (CZTSe) film with low Cu content (Cu/(Zn + Sn) < 0.8). In this work, the growth mechanisms of CZTSe films under different Se vapor composition are investigated by DC-sputtering and a postselenization approach. The composition of Se vapor has important influence on the compactability of the films and the diffusion of elements in the CZTSe films. By adjusting the composition of Se vapor during the selenization process, an optimized two step selenization process is proposed and highly crystallized CZTSe film with low Cu content (Cu/(Zn + Sn) = 0.75) is obtained. Further study of the effect of Cu content on the morphology and photovoltaic performance of the corresponding CZTSe solar cells has shown that the roughness of the CZTSe absorber film increases when Cu content decreases. As a consequence, the reflection loss of CZTSe solar cells reduces dramatically and the short circuit current density of the cells improve from 34.7 mA/cm(2) for Cu/(Zn + Sn) = 0.88 to 38.5 mA/cm(2) for Cu/(Zn + Sn) = 0.75. In addition, the CZTSe solar cells with low Cu content show longer minority carrier lifetime and higher open circuit voltage than the high Cu content devices. A champion performance CZTSe solar cell with 10.4% efficiency is fabricated with Cu/(Zn + Sn) = 0.75 in the CZTSe film without antireflection coating.

X-ray photoemission studies of Zn doped Cu 1- xTl xBa 2Ca 2Cu 3- yZn yO 10- δ ( y = 0, 2.65) superconductors

NASA Astrophysics Data System (ADS)

Khan, Nawazish A.; Mumtaz, M.; Ahadian, M. M.; Iraji-zad, Azam

2007-03-01

The X-ray photoemission (XPS) measurements of Cu 1- xTl xBa 2Ca 2Cu 3- yZn yO 10- δ ( y = 0, 2.65) superconductors have been performed and compared. These studies revealed that the charge state of thallium in the Cu 0.5Tl 0.5Ba 2O 4- δ charge reservoir layer in Zn doped samples is Tl 1+, while it is a mix of Tl 1+ and Tl 2+ in Zn free samples. The binding energy of Ba atoms in the Zn doped samples is shifted to higher energy, which when considered along with the presence of Tl 1+ suggested that it more efficiently directed the carriers to ZnO 2 and CuO 2 planes. The evidence of improved inter-plane coupling witnessed in X-ray diffraction is also confirmed by XPS measurements of Ca atoms in the Zn doped samples. The shift of the valance band spectrum in these Zn doped samples to higher energies suggested that the electrons at the top edge of the valance band were tied to a higher binding energy (relative to samples without Zn doping), which most likely resulted in a much lower energy state of the system in the superconducting state. The stronger superconducting state arising out of these effects is witnessed in the form of increased Tc( R = 0), Jc and the extent of diamagnetism in the final compound.

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

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

Benda, F.; Kouba, J.

1991-03-01

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

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.

Investigation of collision-induced dissociation products and structures of gas-phase [ M·GlyGlyHis-H]+ ( M = Fe, Ni, Cu, and Zn) complexes.

PubMed

Gannamani, Bharathi; Shin, Joong-Won

2017-02-01

Collision-induced dissociation is carried out for electrosprayed [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , [Cu·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + complexes. [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + yield metal-bound peptide sequence ions and dehydrated ions as primary products, whereas [Cu·GlyGlyHis-H] + generates a more extensive series of metal-bound sequence ions and a product arising from the unusual loss of a formaldehyde moiety; dehydration is significantly suppressed for this complex. Density functional theory calculations show that the copper ion-deprotonated peptide binding energy is substantially higher than those in other complexes, suggesting that there is a correlation between ion-ligand binding energy and their fragmentation behavior.

Combustion synthesized copper-ion substituted FeAl2O4 (Cu0.1Fe0.9Al2O4): A superior catalyst for methanol steam reforming compared to its impregnated analogue

NASA Astrophysics Data System (ADS)

Maiti, Sayantani; Llorca, Jordi; Dominguez, Montserrat; Colussi, Sara; Trovarelli, Alessandro; Priolkar, Kaustubh R.; Aquilanti, Giuliana; Gayen, Arup

2016-02-01

A series of copper ion substituted MAl2O4 (M = Mg, Mn, Fe and Zn) spinels is prepared by a single step solution combustion synthesis (SCS) and tested for methanol steam reforming (MSR). The copper ion substituted Cu0.1Fe0.9Al2O4 appears to be the most active, showing ∼98% methanol conversion at 300 °C with ∼5% CO selectivity at GHSV = 30,000 h-1 and H2O:CH3OH = 1.1. The analogous impregnated catalyst, CuO (10 at%)/FeAl2O4, is found to be much less active. These materials are characterized by XRD, H2-TPR, BET, HRTEM, XPS and XANES analyses. Spinel phase formation is highly facilitated upon Cu-ion substitution and Cu loading beyond 10 at% leads to the formation of CuO as an additional phase. The ionic substitution of copper in FeAl2O4 leads to the highly crystalline SCS catalyst containing Cu2+ ion sites that are shown to be more active than the dispersed CuO nano-crystallites on the FeAl2O4 impregnated catalyst, despite its lower surface area. The as prepared SCS catalyst contains also a portion of copper as Cu1+ that increases when subjected to reforming atmosphere. The MSR activity of the SCS catalyst decreases with time-on-stream due to the sintering of catalyst crystallites as established from XPS and HRTEM analyses.

Effect of copper and nickel doping on the optical and structural properties of ZnO

NASA Astrophysics Data System (ADS)

Muǧlu, G. Merhan; Sarıtaş, S.; ćakıcı, T.; Şakar, B.; Yıldırım, M.

2017-02-01

The present study is focused on the Cu doped ZnO and Ni doped ZnO dilute magnetic semiconductor thin films. ZnO:Cu and ZnO:Ni thin films were grown by Chemically Spray Pyrolysis (CSP) method on glass substrates. Optical analysis of the films was done spectral absorption and transmittance measurements by UV-Vis double beam spectrophotometer technique. The structure, morphology, topology and elemental analysis of ZnO:Cu and ZnO:Ni dilute magnetic thin films were investigated by X-ray diffraction (XRD), Raman Analysis, field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM) techniques, respectively. Also The magnetic properties of the ZnO:Ni thin film was investigated by vibrating sample magnetometer (VSM) method. VSM measurements of ZnO:Ni thin film showed that the ferromagnetic behavior.

Copper metallothioneins.

PubMed

Calvo, Jenifer; Jung, Hunmin; Meloni, Gabriele

2017-04-01

Metallothioneins (MTs) are a class of low molecular weight and cysteine-rich metal binding proteins present in all the branches of the tree of life. MTs efficiently bind with high affinity several essential and toxic divalent and monovalent transition metals by forming characteristic polynuclear metal-thiolate clusters within their structure. MTs fulfil multiple biological functions related to their metal binding properties, with essential roles in both Zn(II) and Cu(I) homeostasis as well as metal detoxification. Depending on the organism considered, the primary sequence, and the specific physiological and metabolic status, Cu(I)-bound MT isoforms have been isolated, and their chemistry and biology characterized. Besides the recognized role in the biochemistry of divalent metals, it is becoming evident that unique biological functions in selectively controlling copper levels, its reactivity as well as copper-mediated biochemical processes have evolved in some members of the MT superfamily. Selected examples are reviewed to highlight the peculiar chemical properties and biological functions of copper MTs. © 2016 IUBMB Life, 69(4):236-245, 2017. © 2017 International Union of Biochemistry and Molecular Biology.

Electrospray ionization mass spectrometric investigations of the complexation behavior of macrocyclic thiacrown ethers with bivalent transitional metals (Cu, Co, Ni and Zn).

PubMed

Tsybizova, Alexandra; Tarábek, Ján; Buchta, Michal; Holý, Petr; Schröder, Detlef

2012-10-15

Heavy metals are both a problem for the environment and an important resource for industry. Their selective extraction by means of organic ligands therefore is an attractive topic. The coordination of three thiacrown ethers to late 3d-metal ions was investigated by a combination of electrospray ionization mass spectrometry (ESI-MS) and electron paramagnetic resonance (EPR). The mass spectrometric experiments were carried out in an ion trap mass spectrometer with an ESI source. Absolute binding constants were estimated by comparison with data for 18-crown-6/Na(+). EPR spectroscopy was used as a complementary method for investigating the Cu(I) /Cu(II) redox couple. The study found that thiacrown ethers preferentially bind traces of copper even at an excess of other metal ions (Co(II), Ni(II), and Zn(II)). The absolute association constants of the Cu(I) complexes were about 10(8) M(-1), and about two orders of magnitude lower for the other 3d-metal cations. The EPR spectra demonstrated that the reduction from Cu(II) to Cu(I) upon formation of the [(thiacrown)Cu](+) species takes place in solution. ESI-MS demonstrated that the three thiacrown ligands examined had high binding constants as well as good selectivities for copper(I) at low concentrations, and in the presence of other metal ions. By a combination of ESI-MS and EPR spectrometry it was shown that the reduction from Cu(II) to Cu(I) occurred in solution. Copyright © 2012 John Wiley & Sons, Ltd.

Near room temperature and large-area synthesis of ZnO/Cu2O heterojunction for photocatalytic properties

NASA Astrophysics Data System (ADS)

Gao, Shiyong; Zhang, Jiejing; Li, Wenqiang; Jiao, Shujie; Nie, Yanguang; Fan, Huaiyun; Zeng, Zhi; Yu, Qingjiang; Wang, Jinzhong; Zhang, Xitian

2018-01-01

Large-area ZnO/Cu2O heterojunction have been successfully synthesized on Cu foil through a simple two-step solution method at near room temperature. The field emission scanning electron microscopy characterization indicates that the morphology of as-prepared Cu2O film grown on Cu foil is octahedral structure with diameter of ∼450 nm and ZnO is nanorod arrays structure with diameter of ∼150 nm. The current-voltage measurement of ZnO/Cu2O heterojunction shows a typical rectifying characteristics. Moreover, the photocatalytic test indicates that ZnO/Cu2O heterojunction exhibits high photocatalytic efficient for degradation of congo red dyes. The possible photocatalytic mechanism of ZnO/Cu2O heterojunction is also presented.

Cellular and molecular responses of adult zebrafish after exposure to CuO nanoparticles or ionic copper.

PubMed

Vicario-Parés, Unai; Lacave, Jose M; Reip, Paul; Cajaraville, Miren P; Orbea, Amaia

2018-01-01

Due to their antimicrobial, electrical and magnetic properties, copper nanoparticles (NPs) are suitable for a vast array of applications. Copper can be toxic to biota, making it necessary to assess the potential hazard of copper nanomaterials. Zebrafish (Danio rerio) were exposed to 10 µg Cu/L of CuO NPs of ≈100 nm (CuO-poly) or ionic copper to compare the effects provoked after 3 and 21 days of exposure and at 6 months post-exposure (mpe). At 21 days, significant copper accumulation was only detected in fish exposed to ionic copper. Exposure to both copper forms caused histopathological alterations that could reduce gill functionality, more markedly in the case of ionic copper. Nevertheless, at 6 mpe higher prevalences of gill lesions were detected in fish previously exposed to CuO-poly NPs. No relevant histological alterations were detected in liver, but the lysosomal membrane stability test showed significantly impaired general health status after exposure to both metal forms that lasted up to 6 mpe. 69 transcripts appeared regulated after 3 days of exposure to CuO-poly NPs, suggesting that NPs could produce oxidative stress and reduce metabolism and transport processes. Thirty transcripts were regulated after 21 days of exposure to ionic copper, indicating possible DNA damage. Genes of the circadian clock were identified as the key genes involved in time-dependent differences between the two copper forms. In conclusion, each copper form showed a distinct pattern of liver transcriptome regulation, but both caused gill histopathological alterations and long lasting impaired health status in adult zebrafish.

Identification of the copper-zinc superoxide dismutase activity in Mycoplasma hyopneumoniae.

PubMed

Chen, J R; Weng, C N; Ho, T Y; Cheng, I C; Lai, S S

2000-05-11

Copper-zinc superoxide dismutase (Cu/ZnSOD), a key enzyme in defense against toxic oxygen-free radicals, is widespread in eukaryotes and several species of gram-negative bacteria. The presence of this enzyme in Mycoplasma hyopneumoniae (M. hyopneumoniae), the primary pathogen of mycoplasmal pneumonia in pigs, was examined since the polyclonal antibody against bovine Cu/ZnSOD was dominantly cross-reactive with the M. hyopneumoniae Cu/ZnSOD from whole cellular proteins. In situ activity staining on SDS-PAGE showed that the molecular mass of M. hyopneumoniae Cu/ZnSOD in reducing form was approximately 17kDa. The presence of Cu and Zn ions at the active site of the enzyme was confirmed on the basis of inhibition by KCN and by H(2)O(2). The activity of M. hyopneumoniae Cu/ZnSOD on both SDS- and native-polyacrylamide gels was completely inhibited by 2mM KCN and the gels showed no iron-containing SOD (FeSOD) or manganese-containing SOD (MnSOD) in the crude extracts. The activity of M. hyopneumoniae Cu/ZnSOD in crude extract was 70units/mg protein and was 55% inhibited by 5mM KCN and 56% inactivated by 40mM H(2)O(2). This enzyme was growth-stage dependent and evidenced markedly higher production during the early log phase. Different expression levels of Cu/ZnSOD activity in field isolates were also detected. Taken together, the presence of Cu/ZnSOD in M. hyopneumoniae was identified for the first time.

In vitro chemical and biological effects of Ag, Cu and Cu + Zn adjunction in 46S6 bioactive glasses

NASA Astrophysics Data System (ADS)

Bunetel, L.; Wers, E.; Novella, A.; Bodin, A.; Pellen-Mussi, P.; Oudadesse, H.

2015-09-01

Three bioactive glasses belonging to the system SiO2-CaO- Na2O-P2O5 elaborated by conventional melt-quenching techniques were doped with silver, copper and copper + zinc. They were characterized using the usual physical methods. Human osteoblast cells Saos-2 and human endothelial cells EAhy926 were used for viability assays and to assess the metallic ions, self toxicity. Human monocyte cells THP-1 were used to measure interleukins IL1β and IL6 release. Glass chemical structures did not vary much on introduction of metal ions. A layer of hydroxyapatite was observed on every glass after 30 days of SBF immersion. A proliferative action was seen on Saos-2 after 24 h of incubation, EAhy926 growth was not affected. For both cell lines, a moderate cytotoxicity was found after 72 h. Dose-dependent toxic effects of Ag, Cu and Zn ions were observed on Saos-2 and EAhy926 cells. Measured CD50 of silver against these two cell lines were 8 to 20 fold lower than copper and zinc’s. Except undoped control glass, all doped glasses tested showed anti-inflammatory properties by preventing IL1β and IL6 excretion by differentiated THP-1. In conclusion, strictly monitored adjunction of metal ions to bioglasses ensures good anti-inflammatory properties without altering their biocompatibility.

Synergies between Unsaturated Zn/Cu Doping Sites in Carbon Dots Provide New Pathways for Photocatalytic Oxidation

DOE PAGES

Wu, Wenting; Zhang, Qinggang; Wang, Ruiqin; ...

2017-12-07

Unsaturated metal species (UMS) confined in nanomaterials play important roles for electron transfer in a wide range of catalytic reactions. However, the limited fabrication methods of UMS restrict their wider catalytic applications. Here in this paper, we report on the synergy of unsaturated Zn and Cu dopants confined in carbon dots (ZnCu-CDs) to produce enhanced electron transfer and photooxidation processes in the doped CDs. The Zn/Cu species chelate with the carbon matrix mainly through Cu-O(N)-Zn-O(N)-Cu complexes. Within this structure, Cu 2+ acts as a mild oxidizer that facilely increases the unsaturated Zn content and also precisely tunes the unsaturated Znmore » valence state to Zn d+, where d is between 1 and 2, instead of Zn. With the help of UMS, electron-transfer pathways are produced, enhancing both the electron donating (7.0 times) and-accepting (5.3 times) abilities relative to conventional CDs. Because of these synergistic effects, the photocatalytic efficiency of CDs in photooxidation reactions is shown to improve more than 5-fold.« less

Point defects in Cu 2 ZnSnSe 4 (CZTSe): Resonant X-ray diffraction study of the low-temperature order/disorder transition: Point defects in Cu 2 ZnSnSe 4 (CZTSe)

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

Schelhas, L. T.; Stone, K. H.; Harvey, S. P.

The interest in Cu2ZnSn(S,Se)4 (CZTS) for photovoltaic applications is motivated by similarities to Cu(In,Ga)Se2 while being comprised of non-toxic and earth abundant elements. However, CZTS suffers from a Voc deficit, where the Voc is much lower than expected based on the band gap, which may be the result of a high concentration of point-defects in the CZTS lattice. Recently, reports have observed a low-temperature order/disorder transition by Raman and optical spectroscopies in CZTS films and is reported to describe the ordering of Cu and Zn atoms in the CZTS crystal structure. To directly determine the level of Cu/Zn ordering, wemore » have used resonant-XRD, a site, and element specific probe of long range order. We used CZTSe films annealed just below and quenched from just above the transition temperature; based on previous work, the Cu and Zn should be ordered and highly disordered, respectively. Our data show that there is some Cu/Zn ordering near the low temperature transition but significantly less than high chemical order expected from Raman. To understand both our resonant-XRD results and the Raman results, we present a structural model that involves antiphase domain boundaries and accommodates the excess Zn within the CZTS lattice.« less

Evidences for Cu and Zn Isotope Fractionation in Sediments and Particulate Suspended Matter of the Scheldt Estuary

NASA Astrophysics Data System (ADS)

Petit, J.; Mattielli, N.; de Jong, J.; Chou, L.

2004-05-01

Recent developments in MC-ICP-MS technology allow high precision measurements of heavy stable isotopes, such as Cu and Zn isotopes, which have been shown to undergo biotic or abiotic fractionation (1). Application of Zn isotopes to the study of aquatic ecosystems has already shown some interesting perspectives in their potential use as biogeochemical tracers in deep ocean carbonates (2) or Fe-Mn nodules (3). However, until now no investigation of possible Cu and Zn isotopic fractionation has been carried out within estuaries that are important pathways for hydrological and geochemical cycling of metals. Cu and Zn isotope geochemistry has been studied in sandy to loamy surface sediments (top 20 cm) and in suspended particulate matter (SPM) along a transect in a strong tidal estuary, the Scheldt estuary situated in Belgium and the Netherlands (November 2002). Further to separation of Cu, Fe and Zn by one step ion-exchange chromatography, Cu and Zn isotopic ratios are measured with a "Nu-Plasma" MC-ICP-MS. Instrumental mass bias is corrected using reference materials (Zn JMC, Cu NIST SRM 976 and Ga JMC standard) by simultaneous standard-sample bracketing and external normalization (500 ppb Zn doping for Cu isotopic analyses in static mode and 250 ppb Ga doping for Zn isotopic analyses in dynamic mode), together with a Ni correction. These methods lead to long-term reproducibility (2σ at 95 % confidence level) of ± 0.07 per mil for δ 66Zn (n=100 over 7 analysis sessions) and ± 0.06 per mil for δ 65Cu (n=120 over 8 analysis sessions) for 500 ppb of reference material. Average beam intensities are 6 V/ppm. Precise and reproducible results are obtained for concentration as low as 100 ppb for Cu and Zn. Expected Cu and Zn enrichment in SPM (120 ppm and 1200 ppm respectively) and sediments (being 6 to 10 times lower than SPM) in the upper estuary and progressive decrease in metal content by mixing downstream of the maximum turbidity zone (MTZ, around 5 psu) are

Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(i) acetylides†

PubMed Central

Hein, Jason E.

2011-01-01

Copper-catalyzed azide–alkyne cycloaddition (CuAAC) is a widely utilized, reliable, and straightforward way for making covalent connections between building blocks containing various functional groups. It has been used in organic synthesis, medicinal chemistry, surface and polymer chemistry, and bioconjugation applications. Despite the apparent simplicity of the reaction, its mechanism involves multiple reversible steps involving coordination complexes of copper(i) acetylides of varying nuclearity. Understanding and controlling these equilibria is of paramount importance for channeling the reaction into the productive catalytic cycle. This tutorial review examines the history of the development of the CuAAC reaction, its key mechanistic aspects, and highlights the features that make it useful to practitioners in different fields of chemical science. PMID:20309487

Facile synthesis of core-shell Cu2O@ ZnO structure with enhanced photocatalytic H2 production

NASA Astrophysics Data System (ADS)

Zhang, Yong-Hui; Jiu, Bei-Bei; Gong, Fei-Long; Lu, Kuan; Jiang, Nan; Zhang, Hao-Li; Chen, Jun-Li

2018-05-01

Core-shell Cu2O@ZnO composites were synthesized successfully based on a one-pot hydrothermal method in the presence of dioctyl sulfosuccinate sodium salt (AOT) surfactant. The Cu2O can be converted to rough core-shell Cu2O@ZnO structure by adjusting the amount of zinc powder added. The as-synthesized Cu2O@ZnO composites exhibited excellent photocatalytic activity and the amount of H2 generated using these composites was 4.5-fold more than that produced with Cu2O cubes. A possible photocatalytic mechanism for the Cu2O@ZnO composites with enhanced photocatalytic activity could be the separation by ZnO of the effective charge carriers.

BariumCopperChFluorine (Ch = Sulfur, Selenium, Tellurium) p-type transparent conductors

NASA Astrophysics Data System (ADS)

Zakutayev, Andriy

BaCuChF (Ch = S, Se, Te) materials are chalcogen-based transparent conductors with wide optical band gaps (2.9 -- 3.5 eV) and a high concentration of free holes (1018 -- 1020 cm-3 ) caused by the presence of copper vacancies. Chalcogen vacancies compensate copper vacancies in these materials, setting the Fermi level close to the valence band maximum. BaCuChF thin film solid solutions prepared by pulsed laser deposition (PLD) have tunable properties, such as lattice constants, conductivity and optical band gaps. BaCuSF and BaCuSeF materials also feature room-temperature stable 3D excitons with spin-orbit-split levels. BaCuTeF has forbidden lowest-energy optical transitions which extends its transparency range. BaCuChF surfaces oxidize when exposed to air, but can be protected using Ch capping layers. Polycrystalline BaCuSeF thin films have a 4.85 eV work function, a 0.11 eV hole injection barrier into ZnPc, and 0.00 eV valence band offset with ZnTe. BaCuSeF should have s similar band offset and similar interfacial properties with CdTe and Cu(InGa)Se2, and BaCuSF should have no valence band offset with Cu2ZnSnS4, according to the transitivity rule. Therefore, BaCuSeF is suitable for applications as a p-layer in organic light-emitting diodes, p-i-n double-heterojunction and tandem chalcogenide solar cells.

Different routes to methanol: Inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts

DOE PAGES

Kandemir, Timur; Friedrich, Matthias; Parker, Stewart F.; ...

2016-04-14

We have investigated methanol synthesis with model supported copper catalysts, Cu/ZnO and Cu/MgO, using CO/H 2 and CO 2/H 2 as feedstocks. Under CO/H 2 both catalysts show chemisorbed methoxy as a stable intermediate, the Cu/MgO catalyst also shows hydroxyls on the support. Under CO 2/H 2 the catalysts behave differently, in that formate is also seen on the catalyst. For the Cu/ZnO catalyst hydroxyls are present on the metal whereas for the Cu/MgO hydroxyls are found on the support. Furthermore, these results are consistent with a recently published model for methanol synthesis and highlight the key role of ZnOmore » in the process.« less

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu{sup -}(cytidine) and Cu{sup -}(uridine)

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

Li Xiang; Ko, Yeon-Jae; Wang Haopeng

2011-02-07

The copper-nucleoside anions, Cu{sup -}(cytidine) and Cu{sup -}(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu{sup -}(cytidine) and Cu{sup -}(uridine), respectively. According to our calculations, Cu{sup -}(cytidine) and Cu{sup -}(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostaticmore » interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu{sup -}(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.« less

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

The determination of extinction coefficient of CuInS2, and ZnCuInS3 multinary nanocrystals.

PubMed

Qin, Lei; Li, Dongze; Zhang, Zhuolei; Wang, Kefei; Ding, Hong; Xie, Renguo; Yang, Wensheng

2012-10-21

A pioneering work for determining the extinction coefficient of colloidal semiconductor nanocrystals (NCs) has been cited over 1500 times (W. Yu, W. Guo, X. G. Peng, Chem. Mater., 2003, 15, 2854-2860), indicating the importance of calculating NC concentration for further research and applications. In this study, the size-dependent nature of the molar extinction coefficient of "greener" CuInS(2) and ZnCuInS(3) NCs with emission covering the whole visible to near infrared (NIR) is presented. With the increase of NC size, the resulting quantitative values of the extinction coefficients of ternary CuInS(2) and quaternary ZnCuInS(3) NCs are found to follow a power function with exponents of 2.1 and 2.5, respectively. Obviously, a larger value of extinction coefficient is observed in quaternary NCs for the same size of particles. The difference of the extinction coefficient from both samples is clearly demonstrated due to incorporating ZnS with a much larger extinction coefficient into CuInS(2) NCs.

(Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5}, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

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

Salamakha, Leonid P.; Sologub, Oksana, E-mail: oksana.sologub@univie.ac.at; Stöger, Berthold

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt{sub 1−x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.33) forms a B-filled β-Mn-type structure (space group P4{sub 1}32; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt{sub 9}Cu{sub 3}B{sub 5} (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt{sub 9}Zn{submore » 3}B{sub 5–δ}-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt{sub 6}] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt{sub 6}] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt{sub 6}] and [Pt{sub 6}] trigonal prisms, rotated perpendicularly to the central one. There is no B–B contact as well as Cu–B contact in the structure. The relationships of Pt{sub 9}Cu{sub 3}B{sub 5} structure with the structure of Ti{sub 1+x}Os{sub 2−x}RuB{sub 2} as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ{sub 0}H{sub C2}(0){sup WHH} of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt{sub 9}Cu{sub 3}B{sub 5} (Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure) from electrical resistivity measurements. - Highlights: • First two copper platinum borides, (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu

Phytotoxic effects of Cu and Zn on soybeans grown in field-aged soils: their additive and interactive actions.

PubMed

Kim, Bojeong; McBride, Murray B

2009-01-01

A field pot experiment was conducted to investigate the interactive phytotoxicity of soil Cu and Zn on soybean plants [Glycine max (L.) Merr.]. Two soils (Arkport sandy loam [coarse-loamy, mixed, active, mesic Lamellic Hapludalf] and Hudson silty clay loam [fine, illitic, mesic Glossaquic Hapludalf]) spiked with Cu, Zn, and combinations of both to reach the final soil metal range of 0 to 400 mg kg(-1) were tested in a 2-yr bioassay after 1 yr of soil-metal equilibration in the field. The soluble and easily-extractable fraction of soil Zn (or Cu), estimated by dilute CaCl2, increased linearly in response to the total Zn (or Cu) added. This linearity was, however, strongly affected where soils were treated with both metals in combination, most notably for Zn, as approximately 50% more of soil Zn was extracted into solution when the Cu level was high. Consequently, added Zn is less likely to be stabilized by aging than added Cu when both metals are present in field soils. The predictive model relating soil metal extractability to plant Zn concentration also revealed a significant Cu-Zn interaction. By contrast, the interaction between the two metals contributed little to explain plant Cu uptake. The additive action of soil Cu and Zn was of considerable importance in explaining plant biomass reduction. This work clearly demonstrates the critical roles of the properties of the soil, the nature of the metal, and the level of other toxic metals present on the development of differential phytotoxicity due to soil Cu and Zn.

Age-dependent changes of cerebral copper metabolism in Atp7b -/- knockout mouse model of Wilson's disease by [64Cu]CuCl2-PET/CT.

PubMed

Xie, Fang; Xi, Yin; Pascual, Juan M; Muzik, Otto; Peng, Fangyu

2017-06-01

Copper is a nutritional metal required for brain development and function. Wilson's disease (WD), or hepatolenticular degeneration, is an inherited human copper metabolism disorder caused by a mutation of the ATP7B gene. Many WD patients present with variable neurological and psychiatric symptoms, which may be related to neurodegeneration secondary to copper metabolism imbalance. The objective of this study was to explore the feasibility and use of copper-64 chloride ([ 64 C]CuCl 2 ) as a tracer for noninvasive assessment of age-dependent changes of cerebral copper metabolism in WD using an Atp7b -/- knockout mouse model of WD and positron emission tomography/computed tomography (PET/CT) imaging. Continuing from our recent study of biodistribution and radiation dosimetry of [ 64 C]CuCl 2 in Atp7b -/- knockout mice, PET quantitative analysis revealed low 64 Cu radioactivity in the brains of Atp7b -/- knockout mice at 7th weeks of age, compared with 64 Cu radioactivity in the brains of age- and gender-matched wild type C57BL/6 mice, at 24 h (h) post intravenous injection of [ 64 C]CuCl 2 as a tracer. Furthermore, age-dependent increase of 64 Cu radioactivity was detected in the brains of Atp7b -/- knockout mice from the 13th to 21th weeks of age, based on the data derived from a longitudinal [ 64 C]CuCl 2 -PET/CT study of Atp7b -/- knockout mice with orally administered [ 64 Cu]CuCl 2 as a tracer. The findings of this study support clinical use of [ 64 Cu]CuCl 2 -PET/CT imaging as a tool for noninvasive assessment of age-dependent changes of cerebral copper metabolism in WD patients presenting with variable neurological and psychiatric symptoms.

Effect of Cu2+ substitution on the magnetic properties of co-precipitated Ni-Cu-Zn ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ramakrishna, K. S.; Srinivas, Ch.; Tirupanyam, B. V.; Ramesh, P. N.; Meena, S. S.; Potukuchi, D. M.; Sastry, D. L.

2017-05-01

Spinel ferrite nanoparticles with chemical equation NixCu0.1Zn0.9-xFe2O4 (x = 0.5, 0.6, 0.7) have been synthsized using co-precipitation method followed by heat treatment at a temperature of 200 °C for 2h. The results of XRD, FE-SEM and VSM studies are reported. XRD patterns confirm the formation of cubic spinel phase of ferrite samples along with small amount of a secondary phase of α-Fe2O3 whose concentration decreases as Ni2+ concentration increases. The crystallite sizes (in the range of 7.5-13.9 nm) increase and the lattice parameter decreases with increase in Ni2+ ion concentration. These values are comparable to those of NiZn ferrite without Cu substitution. It has been observed that there is a considerable reduction in saturation magnetisation (Ms). This and differences in other magnetic parameters are attributed to considerable changes in cation distribution or core shell interactions of NiZn ferrite with 10 mole% Cu substitution in the place of Zn.

Influence of CuSO4 and chelated copper algaecide exposures on biodegradation of microcystin-LR.

PubMed

Iwinski, Kyla J; Rodgers, John H; Kinley, Ciera M; Hendrikse, Maas; Calomeni, Alyssa J; McQueen, Andrew D; Geer, Tyler D; Liang, Jenny; Friesen, Vanessa; Haakensen, Monique

2017-05-01

Copper exposures from algaecide applications in aquatic systems are hypothesized to impede bacterial degradation of microcystin (MC), a cyanobacterial produced hepatotoxin. Despite regulatory implications of this hypothesis, limited data exist on influences of copper-exposures on MC-degrading bacteria and consequent MC-degradation. In this study, influences of copper-algaecide concentrations and formulations on bacterial composition and microcystin-LR (MCLR) degradation were investigated. Microcystis aeruginosa was exposed to four concentrations (0-5.0 mg Cu L -1 ) of three copper-algaecide formulations, and rates and extents of MCLR degradation were measured. In untreated controls and following exposures of 0.1, 0.5, and 1.0 mg Cu L -1 , MCLR concentrations decreased at a rate of ∼41-53 μg MCLR/L d -1 . Following exposure to 5.0 mg Cu L -1 MCLR degradation rates decreased an order of magnitude to ∼3-7 μg MCLR/L d -1 . Bacterial diversity decreased following copper-exposures greater than 0.1 mg Cu L -1 for all formulations. Relative abundance of certain groups of MC-degrading bacteria identified in treatments increased with increasing copper concentration, suggesting they may be less sensitive to copper exposures than other, MCLR and non MC-degrading heterotrophic bacteria present in the assemblage. Results from this study revealed that copper concentration can influence degradation rates of MCLR, however this influence was not significant within copper concentrations currently registered for use (≤1.0 mg Cu L -1 ) of the tested algaecides. Copper formulation did not significantly alter degradation rates or bacterial composition. These data augment our understanding of the influences of copper algaecide-exposures on MCLR degradation, and can be used to inform more accurate risk evaluations and use of copper-algaecides for management of MCLR-producing cyanobacteria. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical and optical characterization of cobalt, copper and zinc phthalocyanine complexes.

PubMed

Lee, Jaehyun; Kim, Se Hun; Lee, Woosung; Lee, Jiwon; An, Byeong-Kwan; Oh, Se Young; Kim, Jae Pil; Park, Jongwook

2013-06-01

New phthalocyanine (Pc) derivatives that include the alkyl group in ligand were synthesized based on three core metals such as zinc (Zn), copper (Cu), and cobalt (Co). Electrochemical behaviors and optical properties of the new phthalocyanine derivatives with ligand and different core metal were investigated by using cyclic voltammetry, UV-Visible (UV-Vis) spectroscopy and photoluminescence (PL) spectroscopy. In UV-Vis data, maximum values of 2H, Co, Cu, and Zn complexes were 708 nm and 677 nm, 686 nm, 684 nm, respectively.

Development of self-powered strain sensor using mechano-luminescent ZnS:Cu and mechano-optoelectronic P3HT

NASA Astrophysics Data System (ADS)

Pulliam, Elias; Hoover, George; Tiparti, Dhruv; Ryu, Donghyeon

2017-04-01

Aerospace structural systems are prone to structural damage during their use by vibration, impact, material degradation, and other factors. Due to the harsh environments in which aerospace structures operate, aerospace structures are susceptible to various types of damage and often their structural integrity is jeopardized unless damage onset is detected in timely manner. Yet, current state-of-the-art sensor technologies are still limited for structural health monitoring (SHM) of aerospace structures due to their high power consumption, need for large form factor design, and manageable integration into aerospace structures. This study proposes a design of multilayered self-powered strain sensor by coupling mechano-luminescent (ML) property of copper-doped zinc sulfide (ZnS:Cu) and mechano-optoelectronic (MO) property of poly(3-hexylthiophene) (P3HT). One functional layer of the self-powered strain sensor is ZnS:Cu-based elastomeric composites that emit light in response to mechanical deformation. Another functional layer is P3HT-based thin films that generate direct current (DC) under light illumination and DC magnitude changes with applied strain. First, ML light emission characteristics of ZnS:Cu-based composites are studied under cyclic tensile strain with two various maximum strain up to 10% and 15% at various loading frequencies from 5 Hz to 20 Hz. Second, piezo-optical properties of P3HT-based thin films are investigated by acquiring light absorption of the thin films at various strains from 0% to 2% tensile strain. Last, micro-mechanical properties of the P3HT-based thin films are characterized using nanoindentation.

Is a high serum copper concentration a risk factor for implantation failure?

PubMed

Matsubayashi, Hidehiko; Kitaya, Kotaro; Yamaguchi, Kohei; Nishiyama, Rie; Takaya, Yukiko; Ishikawa, Tomomoto

2017-08-10

Copper-containing contraceptive devices may deposit copper ions in the endometrium, resulting in implantation failure. The deposition of copper ions in many organs has been reported in patients with untreated Wilson's disease. Since these patients sometimes exhibit subfertility and/or early pregnancy loss, copper ions were also considered to accumulate in the uterine endometrium. Wilson's disease patients treated with zinc successfully delivered babies because zinc interfered with the absorption of copper from the gastrointestinal tract. These findings led to the hypothesis that infertile patients with high serum copper concentrations may have implantation failure due to the excess accumulation of copper ions. The relationship between implantation (pregnancy) rates and serum copper concentrations has not yet been examined. The Japanese government recently stated that actual copper intake was higher among Japanese than needed. Therefore, the aim of the present study was to investigate whether serum copper concentrations are related to the implantation (pregnancy) rates of human embryos in vivo. We included 269 patients (age <40 years old) who underwent vitrifying and warming single embryo transfer with a hormone replacement cycle using good blastocysts (3BB or more with Gardner's classification). Serum hCG, copper, and zinc concentrations were measured 16 days after the first date of progesterone replacement. We compared 96 women who were pregnant without miscarriage at 10 weeks of gestation (group P) and 173 women who were not pregnant (group NP). No significant differences were observed in age or BMI between the groups. Copper concentrations were significantly higher in group NP (average 193.2 μg/dL) than in group P (average 178.1 μg/dL). According to the area under the curve (AUC) on the receiver operating characteristic curve for the prediction of clinical pregnancy rates, the Cu/Zn ratio (AUC 0.64, 95% CI 0.54-0.71) was a better predictor than copper or

Circulating copper and zinc levels and risk of hepatobiliary cancers in Europeans

PubMed Central

Stepien, Magdalena; Hughes, David J; Hybsier, Sandra; Bamia, Christina; Tjønneland, Anne; Overvad, Kim; Affret, Aurélie; His, Mathilde; Boutron-Ruault, Marie-Christine; Katzke, Verena; Kühn, Tilman; Aleksandrova, Krasimira; Trichopoulou, Antonia; Lagiou, Pagona; Orfanos, Phlippos; Palli, Domenico; Sieri, Sabina; Tumino, Rosario; Ricceri, Fulvio; Panico, Salvatore; Bueno-de-Mesquita, H B(as); Peeters, Petra H; Weiderpass, Elisabete; Lasheras, Cristina; Bonet Bonet, Catalina; Molina-Portillo, Elena; Dorronsoro, Miren; Huerta, José María; Barricarte, Aurelio; Ohlsson, Bodil; Sjöberg, Klas; Werner, Mårten; Shungin, Dmitry; Wareham, Nick; Khaw, Kay-Tee; Travis, Ruth C; Freisling, Heinz; Cross, Amanda J; Schomburg, Lutz; Jenab, Mazda

2017-01-01

Background: Copper and zinc are essential micronutrients and cofactors of many enzymatic reactions that may be involved in liver-cancer development. We aimed to assess pre-diagnostic circulating levels of copper, zinc and their ratio (Cu/Zn) in relation to hepatocellular carcinoma (HCC), intrahepatic bile duct (IHBD) and gall bladder and biliary tract (GBTC) cancers. Methods: A nested case–control study was conducted within the European Prospective Investigation into Cancer and Nutrition cohort. Serum zinc and copper levels were measured in baseline blood samples by total reflection X-ray fluorescence in cancer cases (HCC n=106, IHDB n=34, GBTC n=96) and their matched controls (1:1). The Cu/Zn ratio, an indicator of the balance between the micronutrients, was computed. Multivariable adjusted odds ratios and 95% confidence intervals (OR; 95% CI) were used to estimate cancer risk. Results: For HCC, the highest vs lowest tertile showed a strong inverse association for zinc (OR=0.36; 95% CI: 0.13–0.98, Ptrend=0.0123), but no association for copper (OR=1.06; 95% CI: 0.45–2.46, Ptrend=0.8878) in multivariable models. The calculated Cu/Zn ratio showed a positive association for HCC (OR=4.63; 95% CI: 1.41–15.27, Ptrend=0.0135). For IHBC and GBTC, no significant associations were observed. Conclusions: Zinc may have a role in preventing liver-cancer development, but this finding requires further investigation in other settings. PMID:28152549

Different dietary lifestyles and serum zinc and copper in women of reproductive age

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

Breskin, M.W.; Worthington-Roberts, B.S.; Monsen, E.R.

1986-03-01

Nutrient intakes and biochemical measures of zinc and copper were compared in non-pregnant young women representing different dietary lifestyles, viz, those who habitually ate red meat (RM), fish or poultry (FP), or lacto-ovo-vegetarian (LV) sources of protein. All were in good health and concerned about their diets; none was using supplements or oral contraceptives. Three-day food records were analyzed for nutrient content. Serum and drinking water samples were assayed for zinc and copper (AAS), and serum, for ceruloplasmin (RID). Sign. diff. in dietary Zn or Cu content were not reflected by serum(Zn) or (Cu), but the incidence of serum(Zn) Zn).« less

Effects of Zn²⁺ and Cu²⁺ on loach ovaries and ova development.

PubMed

Tang, Jian-Xun; Li, Jun-Rong; Liu, Zhong-Liang; Zhao, Hua; Tao, Xiao-Min; Cheng, Zhang-Shun

2013-10-01

This study compared the accumulation of Zn²⁺ and Cu²⁺ in the ovaries and ova of loaches under different concentrations of Zn²⁺ (1.00, 2.50 and 5.00 mg/L respectively) and Cu²⁺ (0.10, 0.25 and 0.50 mg/L respectively). The results showed that both Zn²⁺ and Cu²⁺ accumulated in the ovaries, and that the relationship between accumulation and time was linear over 20 days of exposure. The accumulation of the metals in ovaries was closely related to the concentration of exposure in the solutions (P<0.05), and was obviously affected by the time and doses. However, the Cu²⁺ concentration was significantly higher than Zn²⁺ (P<0.05). The development level of ova in the ovaries also correlated with the concentration and exposure period in the Zn²⁺ and Cu²⁺ solutions. This study compared the accumulation of Zn 2+ and Cu 2+ in the ovaries and ova of loaches under different concentrations of Zn 2+ (1.00, 2.50 and 5.00 mg/L respectively) and Cu 2+ (0.10, 0.25 and 0.50 mg/L respectively). The results showed that both Zn 2+ and Cu 2+ accumulated in the ovaries, and that the relationship between accumulation and time was linear over 20 days of exposure. The accumulation of the metals in ovaries was closely related to the concentration of exposure in the solutions ( P< 0.05), and was obviously affected by the time and doses. However, the Cu 2+ concentration was significantly higher than Zn 2+ ( P< 0.05). The development level of ova in the ovaries also correlated with the concentration and exposure period in the Zn 2+ and Cu 2+ solutions.

Synthesis and photoelectrochemical properties of a novel CuO/ZnO nanorod photocathode for solar hydrogen generation

NASA Astrophysics Data System (ADS)

Shaislamov, Ulugbek; Lee, Heon-Ju

2016-10-01

Here, we present a facile synthesis method and photoelectrochemical characterizations of a p-type CuO-nanorod array photoelectrode with ZnO nanorod branches. Vertically-aligned CuO nanorods were synthesized by using direct oxidation of metallic Cu nanorods grown on a Cu substrate by using a facile template-assisted electrodeposition method. The formed CuONR/ZnONB hierarchically-structured photoelectrode exhibited remarkable photoelectrodechemical performance and outstanding stability compared to the CuO NR photoelectrode without ZnO NR branches. Morphological, optical and electrochemical characterizations were carried out in order to examine the effects of ZnO nanorod branches on the stability and the overall electrochemical performance of the electrode.

Copper, Zinc Superoxide Dismutase is Primarily a Cytosolic Protein in Human Cells

NASA Astrophysics Data System (ADS)

Crapo, James D.; Oury, Tim; Rabouille, Catherine; Slot, Jan W.; Chang, Ling-Yi

1992-11-01

The intracellular localization of human copper, zinc superoxide dismutase (Cu,Zn-SOD; superoxide:superoxide oxidoreductase, EC 1.15.1.1) was evaluated by using EM immunocytochemistry and both isolated human cell lines and human tissues. Eight monoclonal antibodies raised against either native or recombinant human Cu,Zn-SOD and two polyclonal antibodies raised against either native or recombinant human Cu,Zn-SOD were used. Fixation with 2% paraformaldehyde/0.2% glutaraldehyde was found necessary to preserve normal distribution of the protein. Monoclonal antibodies were less effective than polyclonal antibodies in recognizing the antigen after adequate fixation of tissue. Cu,Zn-SOD was found widely distributed in the cell cytosol and in the cell nucleus, consistent with it being a soluble cytosolic protein. Mitochondria and secretory compartments did not label for this protein. In human cells, peroxisomes showed a labeling density slightly less than that of cytoplasm.

Phytoextraction of Zn and Cu from sewage sludge and impact on agronomic characteristics.

PubMed

Xiaomei, Liu; Qitang, Wu; Banks, M K; Ebbs, S D

2005-01-01

The presence of elevated concentrations of heavy metals limits the usage of sewage sludge as a fertilizer and soil amendment. Experiments were carried out to examine the extent to which seven plant species phytoextracted Zn and Cu from dewatered sludge. The hyperaccumulators Thlaspi caerulescens and Sedum alfredii showed the greatest removal of Zn, while shoots and tubers of two species of Alocasia showed the greatest Cu removal. Cultivation of plants in the sludge resulted in significant decreases in total Zn and changes in the partitioning of Zn between soil pools. However, Cu levels were largely unchanged and remained associated predominantly with the organic matter pool. Agronomic characteristics of the sludge material, such as pH, organic matter content, and nitrogen, phosphorus, and potassium concentrations, did not change significantly during the four-month growth period, indicating that subsequent crops could be sustained by this material. These results suggest that Zn can be phytoextracted from sludge material, provided the rate of metal uptake exceeds the rate of mobilization to the exchangeable fraction. Since there was no appreciable accumulation of Zn and Cu in seeds of Zea mays in this study, some tissues from sludge-grown plants could potentially be used as animal fodder.

Synthesis and characterization of Ce, Cu co-doped ZnS nanoparticles

NASA Astrophysics Data System (ADS)

Harish, G. S.; Sreedhara Reddy, P.

2015-09-01

Ce, Cu co-doped ZnS nanoparticles were prepared at room temperature using a chemical co-precipitation method. The prepared nanoparticles were characterized by X- ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive analysis of X-rays (EDAX), diffuse reflectance spectroscopy (DRS), photoluminescence (PL) and high resolution Raman spectroscopic techniques. Transmission electron microscopy (TEM) and X-ray diffraction studies showed that the diameter of the particles was around 2-3 nm. Broadened XRD peaks revealed the formation of nanoparticles with a face centered cubic (fcc) structure. DRS studies confirmed that the band gap increased with an increase in the dopant concentration. The Raman spectra of undoped and Ce, Cu ions co-doped ZnS nanoparticles showed longitudinal optical mode and transverse optical mode. Compared with the Raman modes (276 and 351 cm-1) of undoped ZnS nanoparticles, the Raman modes of Ce, Cu co- doped ZnS nanoparticles were slightly shifted towards lower frequency. PL spectra of the samples showed remarkable enhancement in the intensity upon doping.

Reduced anti-ferromagnetism promoted by Zn 3d 10 substitution at CuO 2 planar sites of Cu 0.5Tl 0.5Ba 2Ca 3Cu 4O 12-δ superconductors

NASA Astrophysics Data System (ADS)

Mumtaz, M.; Khan, Nawazish A.

2009-11-01

The role of charge carriers in ZnO 2/CuO 2 planes of Cu 0.5Tl 0.5Ba 2Ca 3Cu 4-yZn yO 12-δ material in bringing about superconductivity has been explained. Due to suppression of anti-ferromagnetic order with Zn 3d 10 ( S=0) substitution at Cu 3d 9(S={1}/{2}) sites in the inner CuO 2 planes of Cu 0.5Tl 0.5Ba 2Ca 3Cu 4O 12-δ superconductor, the distribution of charge carriers becomes homogeneous and optimum, which is evident from the enhanced superconductivity parameters. The decreased c-axis length with the increase of Zn doping improves interlayer coupling and hence the three dimensional (3D) conductivity in the unit cell is enhanced. Also the softening of phonon modes with the increased Zn doping indicates that the electron-phonon interaction has an essential role in the mechanism of high- Tc superconductivity in these compounds.

Zinc and copper distribution in swine wastewater treated by anaerobic digestion.

PubMed

Cestonaro do Amaral, André; Kunz, Airton; Radis Steinmetz, Ricardo Luís; Justi, Karin Cristiane

2014-08-01

Swine wastewater contain high levels of metals, such as copper and zinc, which can cause a negative impact on the environment. Anaerobic digestion is a process commonly used to remove carbon, and can act on metal availability (e.g., solubility or oxidation state). The present study aimed to evaluate the influence of anaerobic digestion on total Zn and Cu contents, and their chemical fractioning due to the biodegradation of the effluent over different hydraulic retention times (HRTs). The sequential extraction protocol proposed by the Community Bureau of Reference (BCR), plus two additional fractions, was the method chosen for this study of Cu and Zn distribution evaluation in swine wastewater. The Zn and Cu concentrations in raw swine manure were 63.58 ± 27.72 mg L(-1) and 8.98 ± 3.99 mg L(-1), respectively. The metal retention capacity of the bioreactor decreased when the HRT was reduced from 17.86 d to 5.32 d. Anaerobic digestion had a direct influence on zinc and copper distribution when raw manure (RM) and digested manure (DM) were compared. The reducible fraction showed a reduction of between 3.17% and 7.84% for Zn and between 2.52% and 11.92% for Cu when DM was compared with RM. However, the metal concentration increased in the oxidizable fraction of DM, viz. from 3.01% to 10.64% for Zn and from 4.49% to 16.71% for Cu, thus demonstrating the effect of anaerobic conditions on metal availability. Copyright © 2014 Elsevier Ltd. All rights reserved.

64Cu, a powerful positron emitter for immunoimaging and theranostic: Production via natZnO and natZnO-NPs.

PubMed

Karimi, Zahra; Sadeghi, Mahdi; Mataji-Kojouri, Naimeddin

2018-07-01

64 Cu is one of the most beneficial radionuclide that can be used as a theranostic agent in Positron Emission Tomography (PET) imaging. In this current work, 64 Cu was produced with zinc oxide nanoparticles ( nat ZnONPs) and zinc oxide powder ( nat ZnO) via the 64 Zn(n,p) 64 Cu reaction in Tehran Research Reactor (TRR) and the activity values were compared with each other. The theoretical activity of 64 Cu also was calculated with MCNPX-2.6 and the cross sections of this reaction were calculated by using TALYS-1.8, EMPIRE-3.2.2 and ALICE/ASH nuclear codes and were compared with experimental values. Transmission Electronic Microscopy (TEM), Scanning Electronic Microscopy (SEM) and X-Ray Diffraction (XRD) analysis were used for samples characterizations. From these results, it's concluded that 64 Cu activity value with nanoscale target was achieved more than the bulk state target and had a good adaptation with the MCNPX result. Copyright © 2018 Elsevier Ltd. All rights reserved.

Investigations on structural, vibrational and dielectric properties of nanosized Cu doped Mg-Zn ferrites

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

Yadav, Anand; Department of Physics, MEDICAPS Institute of Science and Technology, Pithampur 453331; Rajpoot, Rambabu

2016-05-23

Transition metal Cu{sup 2+} doped Mg-Zn ferrite [Mg{sub 0.5}Zn{sub 0.5-x}Cu{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5)] were prepared by sol gel auto combustion (SGAC) method to probe the structural, vibrational and electrical properties. X-ray diffraction (XRD) pattern reveals a single-phase cubic spinel structure without the presence of any secondary phase corresponding to other structure. The average particle size of the parent Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} is found to be ~29.8 nm and is found to increase with Cu{sup 2+} doping. Progressive reduction in lattice parameter of Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} has been observed due to difference inmore » ionic radii of cations with improved Cu doping. Spinel cubic structure is further confirmed by Raman spectroscopy. Small shift in Raman modes towards higher wave number has been observed in doped Mg-Zn ferrites. The permittivity and dielectric loss decreases at lower doping and increases at higher order doping of Cu{sup 2+}.« less

Ordering of Zn-centered porphyrin and phthalocyanine on TiO2(011): STM studies

PubMed Central

Godlewski, Szymon; Such, Bartosz; Pawlak, Rémy; Hinaut, Antoine; Jöhr, Res; Glatzel, Thilo; Meyer, Ernst; Szymonski, Marek

2017-01-01

Zn(II)phthalocyanine molecules (ZnPc) were thermally deposited on a rutile TiO2(011) surface and on Zn(II)meso-tetraphenylporphyrin (ZnTPP) wetting layers at room temperature and after elevated temperature thermal processing. The molecular homo- and heterostructures were characterized by high-resolution scanning tunneling microscopy (STM) at room temperature and their geometrical arrangement and degree of ordering are compared with the previously studied copper phthalocyanine (CuPc) and ZnTPP heterostructures. It was found that the central metal atom may play some role in ordering and growth of phthalocyanine/ZnTPP heterostructures, causing differences in stability of upright standing ZnPc versus CuPc molecular chains at given thermal annealing conditions. PMID:28144569