The importance of surface functional groups in the adsorption of copper onto walnut shell derived activated carbon.

PubMed

Xie, Ruzhen; Jin, Yan; Chen, Yao; Jiang, Wenju

2017-12-01

In this study, activated carbon (AC) was prepared from walnut shell using chemical activation. The surface chemistry of the prepared AC was modified by introducing or blocking certain functional groups, and the role of the different functional groups involved in the copper uptake was investigated. The structural and chemical heterogeneity of the produced carbons are characterized by Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, Boehm titration method and N 2 /77 K adsorption isotherm analysis. The equilibrium and the kinetics of copper adsorption onto AC were studied. The results demonstrated that the functional groups on AC played an important role in copper uptake. Among various surface functional groups, the oxygen-containing group was found to play a critical role in the copper uptake, and oxidation is the most effective way to improve Cu (II) adsorption onto AC. Ion-exchange was identified to be the dominant mechanism in the copper uptake by AC. Some other types of interactions, like complexation, were also proven to be involved in the adsorption process, while physical force was found to play a small role in the copper uptake. The regeneration of copper-loaded AC and the recovery of copper were also studied to evaluate the reusability of the oxidized AC.

The role of mineral surface chemistry in modified dextrin adsorption.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

2011-05-15

The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of graphite, and thus has more potential for use as a polymer depressant in this separation. Copyright © 2011 Elsevier Inc. All rights reserved.

Catalytic wet peroxide oxidation of aniline in wastewater using copper modified SBA-15 as catalyst.

PubMed

Kong, Liming; Zhou, Xiang; Yao, Yuan; Jian, Panming; Diao, Guowang

2016-01-01

SBA-15 mesoporous molecular sieves modified with copper (Cu-SBA-15) were prepared by pH-adjusting hydrothermal method and characterized by X-ray diffraction, BET, transmission electron microscopy, UV-Vis and (29)Si MAS NMR. The pH of the synthesis gel has a significant effect on the amount and the dispersion of copper on SBA-15. The Cu-SBA-15(4.5) (where 4.5 denotes the pH value of the synthesis gel) modified with highly dispersed copper was used as catalyst for the oxidation of aniline by H2O2. The Cu-SBA-15(4.5) shows a higher catalytic activity compared to CuO on the surface of SBA-15. The influences of reaction conditions, such as initial pH of the aqueous solutions, temperature, as well as the dosages of H2O2 and catalyst were investigated. Under weakly alkaline aqueous solution conditions, the aniline conversion, the H2O2 decomposition and the total organic carbon (TOC) removal could be increased significantly compared to the acid conditions. The percentage of leaching Cu(2+) could be decreased from 45.0% to 3.66% when the initial pH of solution was increased from 5 to 10. The TOC removal could be enhanced with the increases of temperature, H2O2 and catalyst dosage, but the aniline conversion and H2O2 decomposition change slightly with further increasing dosage of catalyst and H2O2. At 343 K and pH 8.0, 100% aniline conversion and 66.9% TOC removal can be achieved under the conditions of 1.0 g/L catalyst and 0.05 mol/L H2O2 after 180 min. Although copper might be slightly leached from catalyst, the homogeneous Cu(2+) contribution to the whole catalytic activity is unimportant, and the highly dispersed copper on SBA-15 plays a dominant role.

Electrochemical preparation of nickel and copper oxides-decorated graphene composite for simultaneous determination of dopamine, acetaminophen and tryptophan.

PubMed

Liu, Bingdi; Ouyang, Xiaoqian; Ding, Yaping; Luo, Liqing; Xu, Duo; Ning, Yanqun

2016-01-01

In the present work, transition metal oxides decorated graphene (GR) have been fabricated for simultaneous determination of dopamine (DA), acetaminophen (AC) and tryptophan (Trp) using square wave voltammetry. Electro-deposition is a facile preparation strategy for the synthesis of nickel oxide (NiO) and copper oxide (CuO) nanoparticles. GR can be modified by using citric acid to produce more functional groups, which is conducive to the deposition of dispersed metal particles. The morphologies and interface properties of the obtained NiO-CuO/GR nanocomposite were examined by scanning electron microscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy. Moreover, the electrochemical performances of the composite film were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The modified electrode exhibited that the linear response ranges for detecting DA, AC and Trp were 0.5-20 μM, 4-400 μM and 0.3-40 μM, respectively, and the detection limits were 0.17 μM, 1.33 μM and 0.1 μM (S/N=3). Under optimal conditions, the sensor displayed high sensitivity, excellent stability and satisfactory results in real samples analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

Covalent modifications of the amyloid beta peptide by hydroxynonenal: Effects on metal ion binding by monomers and insights into the fibril topology.

PubMed

Grasso, G; Komatsu, H; Axelsen, P H

2017-09-01

Amyloid β peptides (Aβ) and metal ions are associated with oxidative stress in Alzheimer's disease (AD). Oxidative stress, acting on ω-6 polyunsaturated fatty acyl chains, produces diverse products, including 4-hydroxy-2-nonenal (HNE), which can covalently modify the Aβ that helped to produce it. To examine possible feedback mechanisms involving Aβ, metal ions and HNE production, the effects of HNE modification and fibril formation on metal ion binding was investigated. Results indicate that copper(II) generally inhibits the modification of His side chains in Aβ by HNE, but that once modified, copper(II) still binds to Aβ with high affinity. Fibril formation protects only one of the three His residues in Aβ from HNE modification, and this protection is consistent with proposed models of fibril structure. These results provide insight into a network of biochemical reactions that may be operating as a consequence of oxidative stress in AD, or as part of the pathogenic process. Copyright © 2016. Published by Elsevier Inc.

Copper ions removal from water using functionalized carbon nanotubes–mullite composite as adsorbent

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

Tofighy, Maryam Ahmadzadeh; Mohammadi, Toraj, E-mail: torajmohammadi@iust.ac.ir

Highlights: • CNTs–mullite composite was prepared via chemical vapor deposition (CVD) method. • The prepared composite was modified with concentrated nitric acid and chitosan. • The modified CNTs–mullite composites were used as novel adsorbents. • Copper ion removal from water by the prepared adsorbents was performed. • Langmuir and Freundlich isotherms and two kinetic models were applied to fit the experimental data. - Abstract: Carbon nanotubes–mullite composite was synthesized by direct growth of carbon nanotubes on mullite particles via chemical vapor deposition method using cyclohexanol and ferrocene as carbon precursor and catalyst, respectively. The carbon nanotubes–mullite composite was oxidized withmore » concentrated nitric acid and functionalized with chitosan and then used as a novel adsorbent for copper ions removal from water. The results demonstrated that modification with concentrated nitric acid and chitosan improves copper ions adsorption capacity of the prepared composite, significantly. Langmuir and Freundlich isotherms and two kinetic models were applied to fit the experimental data. The carbon nanotubes growth on mullite particles to form the carbon nanotubes–mullite composite with further modification is an inherently safe approach for many promising environmental applications to avoid some concerns regarding environment, health and safety. It was found that the modified carbon nanotubes–mullite composite can be considered as an excellent adsorbent for copper ions removal from water.« less

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

PubMed Central

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

2014-01-01

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

Electrochemical determination of 2,4,6-trinitrophenol using a hybrid film composed of a copper-based metal organic framework and electroreduced graphene oxide.

PubMed

Wang, Yong; Cao, Wei; Wang, Luyao; Zhuang, Qianfen; Ni, Yongnian

2018-06-04

A metal organic framework (MOF) of the type copper(II)-1,3,5-benzenetricarboxylic acid (Cu-BTC) was electrodeposited on electroreduced graphene oxide (ERGO) placed on a glassy carbon electrode (GCE). The modified GCE was used for highly sensitive electrochemical determination of 2,4,6-trinitrophenol (TNP). The fabrication process of the modified electrode was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. Differential pulse voltammetry (DPV) demonstrates that the Cu-BTC/ERGO/GCE gives stronger signals for TNP reduction than Cu-BTC/GCE or ERGO/GCE alone. DPV also shows TNP to exhibit three reduction peaks, the first at a potential of -0.42 V (vs. SCE). This potential was selected because the other three similarly-structured compounds (2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol) do not give a signal at this potential. Response is linear in the 0.2 to 10 μM TNP concentration range, with a 0.1 μM detection limit (at S/N = 3) and a 15.98 μA∙μM -1 ∙cm -2 sensitivity under optimal conditions. The applicability of the sensor was evaluated by detecting TNP in spiked tap water and lake water samples. Recoveries ranged between 95 and 101%. Graphical abstract Schematic presentation of an electrochemical sensor that was fabricated by electrodeposition of the metal-organic framework (MOF) of copper(II)-1,3,5-benzenetricarboxylic acid (Cu-BTC) onto the surface of electroreduced graphene oxide (ERGO) modified glassy carbon electrode (GCE). It was applied to sensitive and selective detection of 2,4,6-trinitrophenol (TNP).

Activation of dioxygen by copper metalloproteins and insights from model complexes

PubMed Central

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

2017-01-01

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

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

PubMed

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

2017-04-01

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

Effect of Copper Oxide, Titanium Dioxide, and Lithium Fluoride on the Thermal Behavior and Decomposition Kinetics of Ammonium Nitrate

NASA Astrophysics Data System (ADS)

Vargeese, Anuj A.; Mija, S. J.; Muralidharan, Krishnamurthi

2014-07-01

Ammonium nitrate (AN) is crystallized along with copper oxide, titanium dioxide, and lithium fluoride. Thermal kinetic constants for the decomposition reaction of the samples were calculated by model-free (Friedman's differential and Vyzovkins nonlinear integral) and model-fitting (Coats-Redfern) methods. To determine the decomposition mechanisms, 12 solid-state mechanisms were tested using the Coats-Redfern method. The results of the Coats-Redfern method show that the decomposition mechanism for all samples is the contracting cylinder mechanism. The phase behavior of the obtained samples was evaluated by differential scanning calorimetry (DSC), and structural properties were determined by X-ray powder diffraction (XRPD). The results indicate that copper oxide modifies the phase transition behavior and can catalyze AN decomposition, whereas LiF inhibits AN decomposition, and TiO2 shows no influence on the rate of decomposition. Possible explanations for these results are discussed. Supplementary materials are available for this article. Go to the publisher's online edition of the Journal of Energetic Materials to view the free supplemental file.

Pd-Cu/poly(o-Anisidine) nanocomposite as an efficient catalyst for formaldehyde oxidation

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

Hosseini, Sayed Reza, E-mail: r.hosseini@umz.ac.ir; Raoof, Jahan-Bakhsh; Ghasemi, Shahram

Highlights: • o-Anisidine monomer was electro-polymerized at the pCPE surface in acid medium. • Palladium/copper NPs were prepared by galvanic replacement method at the POA/pCPE. • Pd-Cu NPs showed excellent electrocatalytic activity towards formaldehyde oxidation. • The bimetallic Pd-Cu NPs/POA nanocomposite showed satisfactory long-term stability. - Abstract: In this work, for the first time, the electrocatalytic oxidation of formaldehyde in 0.5 M sulfuric acid solution at spherical bimetallic palladium-copper nanoparticles (Pd-Cu NPs) deposited on the poly (o-Anisidine) film modified electrochemically pretreated carbon paste electrode (POA/pCPE) has been investigated. Highly porous POA film prepared by electropolymerization onto the pCPE was usedmore » as a potent support for deposition of the Pd-Cu NPs. The Pd-Cu NPs were prepared through spontaneous and irreversible reaction via galvanic replacement between Pd{sup II} ions and the Cu{sup 0} particles. The prepared Pd-Cu NPs were characterized by scanning electron microscopy, energy dispersive spectroscopy and electrochemical methods. The obtained results showed that the utilization of Cu nanoparticles and pretreatment technique enhances the electrocatalytic activity of the modified electrode towards formaldehyde oxidation. The influence of several parameters on formaldehyde oxidation as well as stability of the Pd-Cu/POA/pCPE has been investigated.« less

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

PubMed Central

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

2017-01-01

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

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

PubMed

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

2017-08-09

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

Cu@C nanoporous composites containing little copper oxides derived from dimethyl imidazole modified MOF199 as electrocatalysts for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Wei, Xuedong; Li, Na; Zhang, Xianming

2017-12-01

It remains a huge challenge to develop non precious electrocatalysts with high activity to substitute commercial Pt catalysts for hydrogen evolution reactions (HER). Here, the C-Cu-DI and C-Cu materials with the copper based nanoporous carbon structures were synthesized by carbonizing MOF199 and DI-MOF199. The composite structure and HER electrocatalytic properties of the C-Cu-DI and C-Cu materials are studied. The results show that C-Cu-DI and C-Cu samples exhibit good catalytic activity. And C-Cu-DI sample through the addition of Dimethyl imidazole(DI) in the DI-MOF199 precursor has higher electrocatalytic activity than the C-Cu sample. The superior catalytic activity is attributed to the special composite structure of nanoscale deposition particles on the framework with plenty of nano pores and nano copper and few copper oxidation particles distributed or wrapped into the amorphous porous carbon phase. The nano copper and few copper oxidation particles in the C-Cu and C-Cu-DI catalysts maybe provide the more effective catalytic activity sites. The C-Cu-DI composite with large size spherical hollow deposition particles has higher conductivity, better BET surface area and reasonable micro-meso-macro porous distribution, so the overpotentials at the current density of 1 mA cm-2 and 10 mA cm-2 are respectively 270 mV and 390 mV vs. RHE. Although the HER activity has a big gap with commercial platinum catalyst, this study can provide an important experimental exploration for the design of copper based non noble metal/nano porous carbon composite HER electrocatalyst.

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

PubMed Central

2014-01-01

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

Method of fabricating a catalytic structure

DOEpatents

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2009-09-22

A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

Comparative Proteomic Analysis of the Molecular Responses of Mouse Macrophages to Titanium Dioxide and Copper Oxide Nanoparticles Unravels Some Toxic Mechanisms for Copper Oxide Nanoparticles in Macrophages

PubMed Central

Triboulet, Sarah; Aude-Garcia, Catherine; Armand, Lucie; Collin-Faure, Véronique; Chevallet, Mireille; Diemer, Hélène; Gerdil, Adèle; Proamer, Fabienne; Strub, Jean-Marc; Habert, Aurélie; Herlin, Nathalie; Van Dorsselaer, Alain; Carrière, Marie; Rabilloud, Thierry

2015-01-01

Titanium dioxide and copper oxide nanoparticles are more and more widely used because of their catalytic properties, of their light absorbing properties (titanium dioxide) or of their biocidal properties (copper oxide), increasing the risk of adverse health effects. In this frame, the responses of mouse macrophages were studied. Both proteomic and targeted analyses were performed to investigate several parameters, such as phagocytic capacity, cytokine release, copper release, and response at sub toxic doses. Besides titanium dioxide and copper oxide nanoparticles, copper ions were used as controls. We also showed that the overall copper release in the cell does not explain per se the toxicity observed with copper oxide nanoparticles. In addition, both copper ion and copper oxide nanoparticles, but not titanium oxide, induced DNA strands breaks in macrophages. As to functional responses, the phagocytic capacity was not hampered by any of the treatments at non-toxic doses, while copper ion decreased the lipopolysaccharide-induced cytokine and nitric oxide productions. The proteomic analyses highlighted very few changes induced by titanium dioxide nanoparticles, but an induction of heme oxygenase, an increase of glutathione synthesis and a decrease of tetrahydrobiopterin in response to copper oxide nanoparticles. Subsequent targeted analyses demonstrated that the increase in glutathione biosynthesis and the induction of heme oxygenase (e.g. by lovastatin/monacolin K) are critical for macrophages to survive a copper challenge, and that the intermediates of the catecholamine pathway induce a strong cross toxicity with copper oxide nanoparticles and copper ions. PMID:25902355

Properties of Au/Copper oxide nanocomposite prepared by green laser irradiation of the mixture of individual suspensions

NASA Astrophysics Data System (ADS)

Aazadfar, Parvaneh; Solati, Elmira; Dorranian, Davoud

2018-04-01

The fundamental wavelength of a Q-switched pulsed Nd:YAG laser was employed to produce Au and copper oxide nanoparticles via pulsed laser ablation method in water. Different volumetric ratio of nanoparticles were mixed and irradiated by the second harmonic pulses of the Nd:YAG laser to prepare Au/Copper oxide nanocomposite. The experimental investigation was dedicated to study the properties of Au/Copper oxide nanocomposite as a function of volumetric ratio of Au nanoparticles and copper oxide nanoparticles. Nanocomposites of Au and copper oxide were found almost spherical in shape. Adhesion of spherical nanostructure in Au/Copper oxide nanocomposites was decreased with increasing the concentration of Au nanoparticles. Crystalline phase of the Au/Copper oxide nanocomposites differs with the change in the volumetric ratio of Au and copper oxide nanoparticles. The intensity of surface plasmon resonance of Au nanoparticles was decreased after irradiation. Au/Copper oxide nanocomposites suspensions have emissions in the visible range. Results reveal that green laser irradiation of nanoparticle suspensions is an appropriate method to synthesize Au based nanocomposites with controlled composition and size.

Nanowire-Modified Three-Dimensional Electrode Enabling Low-Voltage Electroporation for Water Disinfection.

PubMed

Huo, Zheng-Yang; Xie, Xing; Yu, Tong; Lu, Yun; Feng, Chao; Hu, Hong-Ying

2016-07-19

More than 10% of the people in the world still suffer from inadequate access to clean water. Traditional water disinfection methods (e.g., chlorination and ultraviolet radiation) include concerns about the formation of carcinogenic disinfection byproducts (DBPs), pathogen reactivation, and/or excessive energy consumption. Recently, a nanowire-assisted electroporation-disinfection method was introduced as an alternative. Here, we develop a new copper oxide nanowire (CuONW)-modified three-dimensional copper foam electrode using a facile thermal oxidation approach. An electroporation-disinfection cell (EDC) equipped with two such electrodes has achieved superior disinfection performance (>7 log removal and no detectable bacteria in the effluent). The disinfection mechanism of electroporation guarantees an exceedingly low operation voltage (1 V) and level of energy consumption (25 J L(-1)) with a short contact time (7 s). The low operation voltage avoids chlorine generation and thus reduces the potential of DBP formation. Because of irreversible electroporation damage on cell membranes, no regrowth and/or reactivation of bacteria occurs during storage after EDC treatment. Water disinfection using EDCs has great potential for practical applications.

Biogenic copper oxide nanoparticles synthesis using Tabernaemontana divaricate leaf extract and its antibacterial activity against urinary tract pathogen

NASA Astrophysics Data System (ADS)

Sivaraj, Rajeshwari; Rahman, Pattanathu K. S. M.; Rajiv, P.; Salam, Hasna Abdul; Venckatesh, R.

2014-12-01

This investigation explains the biosynthesis and characterization of copper oxide nanoparticles from an Indian medicinal plant by an eco-friendly method. The main objective of this study is to synthesize copper oxide nanoparticles from Tabernaemontana divaricate leaves through a green chemistry approach. Highly stable, spherical copper oxide nanoparticles were synthesized by using 50% concentration of Tabernaemontana leaf extract. Formation of copper oxide nanoparticles have been characterized by UV-Vis absorption spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM) analysis. All the analyses revealed that copper oxide nanoparticles were 48 ± 4 nm in size. Functional groups and chemical composition of copper oxide were also confirmed. Antimicrobial activity of biogenic copper oxide nanoparticles were investigated and maximum zone of inhibition was found in 50 μg/ml copper oxide nanoparticles against urinary tract pathogen (Escherichia coli).

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.

Fabrication and characterization of superhydrophobic copper fiber sintered felt with a 3D space network structure and their oil-water separation

NASA Astrophysics Data System (ADS)

Hu, Jinyi; Yuan, Wei; Chen, Wenjun; Xu, Xiaotian; Tang, Yong

2016-12-01

This study reports the fabrication of a novel stable superhydrophobic and superoleophylic porous metal material on a copper fiber sintered felt (CFSF) substrate via a simple solution-immersion method. Oxidation and modification times are two important factors related to the level of hydrophobicity; oxidation for 1 h and modification for 24 h are appropriate to build a superhydrophobic CFSF surface with a water contact angle of 152.83° and a kerosene contact angle of 0°. The stability and high temperature resistance of superhydrophobic CFSF were studied. A novel device was designed to measure the water repellent ability of the treated CFSF. The results indicated that the water repellent ability of superhydrophobic CFSF was almost constant after 40 cycles of sanding. Both the water contact angle and the microstructure of the modified CFSF surface remained nearly unchanged after experiencing ultrasonic vibration for 1 min. The modified CFSF surface maintains super hydrophobicity after being treated at 180 °C for 1 h. The separation efficiencies for different types of oils and organic solvents (kerosene, chloroform, n-hexane and gasoline) are more than 96%. The modified CFSF retains a high robustness of separation efficiency even after it is recycled for the separation of kerosene and water for more than 10 times.

Incorporating bioavailability into management limits for copper in sediments contaminated by antifouling paint used in aquaculture.

PubMed

Simpson, Stuart L; Spadaro, David A; O'Brien, Dom

2013-11-01

Although now well embedded within many risk-based sediment quality guideline (SQG) frameworks, contaminant bioavailability is still often overlooked in assessment and management of contaminated sediments. To optimise management limits for metal contaminated sediments, we assess the appropriateness of a range methods for modifying SQGs based on bioavailability considerations. The impairment of reproduction of the amphipod, Melita plumulosa, and harpacticoid copepod, Nitocra spinipes, was assessed for sediments contaminated with copper from antifouling paint, located below aquaculture cages. The measurement of dilute acid-extractable copper (AE-Cu) was found to provide the most useful means for monitoring the risks posed by sediment copper and setting management limits. Acid-volatile sulfide was found to be ineffective as a SQG-modifying factor as these organisms live mostly at the more oxidised sediment water interface. SQGs normalised to %-silt/organic carbon were effective, but the benefits gained were too small to justify this approach. The effectiveness of SQGs based on AE-Cu was attributed to a small portion of the total copper being present in potentially bioavailable forms (typically<10% of the total). Much of the non-bioavailable form of copper was likely present as paint flakes in the form of copper (I) oxide, the active ingredient of the antifoulant formulation. While the concentrations of paint-associated copper are very high in some sediments, as the transformation of this form of copper to AE-Cu appears slow, monitoring and management limits should assess the more bioavailable AE-Cu forms, and further efforts be made to limit the release of paint particles into the environment. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Cu-modified carbon spheres/reduced graphene oxide as a high sensitivity of gas sensor for NO2 detection at room temperature

NASA Astrophysics Data System (ADS)

Su, Zhibin; Tan, Li; Yang, Ruiqiang; Zhang, Yu; Tao, Jin; Zhang, Nan; Wen, Fusheng

2018-03-01

Nitrogen dioxide (NO2) as one of the most serious air pollution is harmful to people's health, therefore high-performance gas sensors is critically needed. Here, Cu-modified carbon spheres/reduced graphene oxide (Cu@CS/RGO) composite have been prepared as NO2 gas sensor material. Carbon sphere in the interlayer of RGO can increase the specific surface area of RGO. Copper nanoparticles decorated on the surface of CS can effectively enhance the adsorption activity of RGO as supplier of free electrons. The experimental results showed that its particular structure improved the gas sensitivity of RGO at different NO2 concentrations at room temperature.

Reflectometry-Ellipsometry Reveals Thickness, Growth Rate, and Phase Composition in Oxidation of Copper.

PubMed

Diaz Leon, Juan J; Fryauf, David M; Cormia, Robert D; Zhang, Min-Xian Max; Samuels, Kathryn; Williams, R Stanley; Kobayashi, Nobuhiko P

2016-08-31

The oxidation of copper is a complicated process. Copper oxide develops two stable phases at room temperature and standard pressure (RTSP): cuprous oxide (Cu2O) and cupric oxide (CuO). Both phases have different optical and electrical characteristics that make them interesting for applications such as solar cells or resistive switching devices. For a given application, it is necessary to selectively control oxide thickness and cupric/cuprous oxide phase volume fraction. The thickness and composition of a copper oxide film growing on the surface of copper widely depend on the characteristics of as-deposited copper. In this Research Article, two samples, copper films prepared by two different deposition techniques, electron-beam evaporation and sputtering, were studied. As the core part of the study, the formation of the oxidized copper was analyzed routinely over a period of 253 days using spectroscopic polarized reflectometry-spectroscopic ellipsometry (RE). An effective medium approximation (EMA) model was used to fit the RE data. The RE measurements were complemented and validated by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and X-ray diffraction (XRD). Our results show that the two samples oxidized under identical laboratory ambient conditions (RTSP, 87% average relative humidity) developed unique oxide films following an inverse-logarithmic growth rate with thickness and composition different from each other over time. Discussion is focused on the ability of RE to simultaneously extract thickness (i.e., growth rate) and composition of copper oxide films and on plausible physical mechanisms responsible for unique oxidation habits observed in the two copper samples. It appears that extended surface characteristics (i.e., surface roughness and grain boundaries) and preferential crystalline orientation of as-deposited polycrystalline copper films control the growth kinetics of the copper oxide film. Analysis based on a noncontact and nondestructive measurement, such as RE, to extract key material parameters is beneficial for conveniently understanding the oxidation process that would ultimately enable copper oxide-based devices at manufacturing scales.

Laboratory evolution of copper tolerant yeast strains

PubMed Central

2012-01-01

Background Yeast strains endowed with robustness towards copper and/or enriched in intracellular Cu might find application in biotechnology processes, among others in the production of functional foods. Moreover, they can contribute to the study of human diseases related to impairments of copper metabolism. In this study, we investigated the molecular and physiological factors that confer copper tolerance to strains of baker's yeasts. Results We characterized the effects elicited in natural strains of Candida humilis and Saccharomyces cerevisiae by the exposure to copper in the culture broth. We observed that, whereas the growth of Saccharomyces cells was inhibited already at low Cu concentration, C. humilis was naturally robust and tolerated up to 1 g · L-1 CuSO4 in the medium. This resistant strain accumulated over 7 mg of Cu per gram of biomass and escaped severe oxidative stress thanks to high constitutive levels of superoxide dismutase and catalase. Both yeasts were then "evolved" to obtain hyper-resistant cells able to proliferate in high copper medium. While in S. cerevisiae the evolution of robustness towards Cu was paralleled by the increase of antioxidative enzymes, these same activities decreased in evolved hyper-resistant Candida cells. We also characterized in some detail changes in the profile of copper binding proteins, that appeared to be modified by evolution but, again, in a different way in the two yeasts. Conclusions Following evolution, both Candida and Saccharomyces cells were able to proliferate up to 2.5 g · L-1 CuSO4 and to accumulate high amounts of intracellular copper. The comparison of yeasts differing in their robustness, allowed highlighting physiological and molecular determinants of natural and acquired copper tolerance. We observed that different mechanisms contribute to confer metal tolerance: the control of copper uptake, changes in the levels of enzymes involved in oxidative stress response and changes in the copper-binding proteome. However, copper elicits different physiological and molecular reactions in yeasts with different backgrounds. PMID:22214286

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

PubMed Central

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

2016-01-01

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

Copper Metal-Organic Framework Nanoparticles Stabilized with Folic Acid Improve Wound Healing in Diabetes.

PubMed

Xiao, Jisheng; Zhu, Yunxiao; Huddleston, Samantha; Li, Peng; Xiao, Baixue; Farha, Omar K; Ameer, Guillermo A

2018-02-27

The successful treatment of chronic nonhealing wounds requires strategies that promote angiogenesis, collagen deposition, and re-epithelialization of the wound. Copper ions have been reported to stimulate angiogenesis; however, several applications of copper salts or oxides to the wound bed are required, leading to variable outcomes and raising toxicity concerns. We hypothesized that copper-based metal-organic framework nanoparticles (Cu-MOF NPs), referred to as HKUST-1, which are rapidly degraded in protein solutions, can be modified to slowly release Cu 2+ , resulting in reduced toxicity and improved wound healing rates. Folic acid was added during HKUST-1 synthesis to generate folic-acid-modified HKUST-1 (F-HKUST-1). The effect of folic acid incorporation on NP stability, size, hydrophobicity, surface area, and copper ion release profile was measured. In addition, cytotoxicity and in vitro cell migration processes due to F-HKUST-1 and HKUST-1 were evaluated. Wound closure rates were assessed using the splinted excisional dermal wound model in diabetic mice. The incorporation of folic acid into HKUST-1 enabled the slow release of copper ions, which reduced cytotoxicity and enhanced cell migration in vitro. In vivo, F-HKUST-1 induced angiogenesis, promoted collagen deposition and re-epithelialization, and increased wound closure rates. These results demonstrate that folic acid incorporation into HKUST-1 NPs is a simple, safe, and promising approach to control Cu 2+ release, thus enabling the direct application of Cu-MOF NPs to wounds.

Determination of kjeldahl nitrogen in fertilizers by AOAC official methods 978.02: effect of copper sulfate as a catalyst.

PubMed

Abrams, Dean; Metcalf, David; Hojjatie, Michael

2014-01-01

In AOAC Official Method 955.04, Nitrogen (Total) in Fertilizers, Kjeldahl Method, fertilizer materials are analyzed using mercuric oxide or metallic mercury HgO or Hg) as a catalyst. AOAC Official Methods 970.02, Nitrogen (Total) in Fertilizers is a comprehensive total nitrogen (including nitrate nitrogen) method adding chromium metal. AOAC Official Method 978.02, Nitrogen (Total) in Fertilizers is a modified comprehensive nitrogen method used to measure total nitrogen in fertilizers with two types of catalysts. In this method, either copper sulfate or chromium metal is added to analyze for total Kjeldahl nitrogen. In this study, the part of AOAC Official Method 978.02 that is for nitrate-free fertilizer products was modified. The objective was to examine the necessity of copper sulfate as a catalyst for the nitrate-free fertilizer products. Copper salts are not environmentally friendly and are considered pollutants. Products such as ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-containing fertilizers such as isobutylene diurea (IBDU), and urea-triazone fertilizer solutions were examined. The first part of the study was to measure Kjeldahl nitrogen as recommended by AOAC Official Method 978.02. The second part of the study was to exclude the addition of copper sulfate from AOAC Official Method 978.02 to examine the necessity of copper sulfate as a catalyst in nitrate-free fertilizers, which was the primary objective. Our findings indicate that copper sulfate can be eliminated from the method with no significant difference in the results for the nitrogen content of the fertilizer products.

High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film

PubMed Central

Primo, Ana; Esteve-Adell, Ivan; Blandez, Juan F.; Dhakshinamoorthy, Amarajothi; Álvaro, Mercedes; Candu, Natalia; Coman, Simona M.; Parvulescu, Vasile I.; García, Hermenegildo

2015-01-01

Metal oxide nanoparticles supported on graphene exhibit high catalytic activity for oxidation, reduction and coupling reactions. Here we show that pyrolysis at 900 °C under inert atmosphere of copper(II) nitrate embedded in chitosan films affords 1.1.1 facet-oriented copper nanoplatelets supported on few-layered graphene. Oriented (1.1.1) copper nanoplatelets on graphene undergo spontaneous oxidation to render oriented (2.0.0) copper(I) oxide nanoplatelets on few-layered graphene. These films containing oriented copper(I) oxide exhibit as catalyst turnover numbers that can be three orders of magnitude higher for the Ullmann-type coupling, dehydrogenative coupling of dimethylphenylsilane with n-butanol and C–N cross-coupling than those of analogous unoriented graphene-supported copper(I) oxide nanoplatelets. PMID:26509224

Removal of sulfur and nitrogen containing pollutants from discharge gases

DOEpatents

Joubert, James I.

1986-01-01

Oxides of sulfur and of nitrogen are removed from waste gases by reaction with an unsupported copper oxide powder to form copper sulfate. The resulting copper sulfate is dissolved in water to effect separation from insoluble mineral ash and dried to form solid copper sulfate pentahydrate. This solid sulfate is thermally decomposed to finely divided copper oxide powder with high specific surface area. The copper oxide powder is recycled into contact with the waste gases requiring cleanup. A reducing gas can be introduced to convert the oxide of nitrogen pollutants to nitrogen.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Highly antifouling and antibacterial performance of poly (vinylidene fluoride) ultrafiltration membranes blending with copper oxide and graphene oxide nanofillers for effective wastewater treatment.

PubMed

Zhao, Chuanqi; Lv, Jinling; Xu, Xiaochen; Zhang, Guoquan; Yang, Yuesuo; Yang, Fenglin

2017-11-01

Innovation and effective wastewater treatment technology is still in great demand given the emerging contaminants frequently spotted from the aqueous environment. By blending with poly (vinylidene fluoride) (PVDF), the strong hydrophilic graphene oxide (GO) and antibacterial copper oxide (Cu x O) were used as nanofillers to develop the novel, highly antifouling composite membranes via phase inversion process in our latest work. The existence and dispersion of GO and Cu x O posed a significant role on morphologies, structures, surface composition and hydrophilicity of the developed composite membranes, confirmed by SEM, TEM, FTIR and XPS in depth characterization. The SEM images showed that the modified membranes presented a lower resistant structure with developed finger-like macrovoids and thin-walled even interconnected sponge-like pores after adding nanofillers, much encouraging membrane permeation. The XPS results revealed that Cu x O contained Cu 2 O and CuO in the developed membrane and the Cu 2 O nanoparticles were dominant accounting for about 79.3%; thus the modified membrane specifically exhibited an efficient antibacterial capacity. Due to the hydrophilic and bactericidal membrane surface, the composite membranes demonstrated an excellent antifouling performance, including higher flux recovery rate, more resistant against accumulated contaminants and lower filtration resistance, especially lower irreversible resistance. The antifouling property, especially anti-irreversible fouling, was significantly improved, showing a significant engineering potential. Copyright © 2017 Elsevier Inc. All rights reserved.

Copper modified carbon molecular sieves for selective oxygen removal

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor); Seshan, Panchalam K. (Inventor)

1992-01-01

Carbon molecular sieves modified by the incorporation of finely divided elemental copper useful for the selective sorption of oxygen at elevated temperatures. The carbon molecular sieves can be regenerated by reduction with hydrogen. The copper modified carbon molecular sieves are prepared by pyrolysis of a mixture of a copper-containing material and polyfunctional alcohol to form a sorbent precursor. The sorbent precursors are then heated and reduced to produce copper modified carbon molecular sieves. The copper modified carbon molecular sieves are useful for sorption of all concentrations of oxygen at temperatures up to about 200.degree. C. They are also useful for removal of trace amount of oxygen from gases at temperatures up to about 600.degree. C.

Cytoprotective properties of a fullerene derivative against copper

NASA Astrophysics Data System (ADS)

Ratnikova, Tatsiana A.; Bebber, Mark J.; Huang, George; Larcom, Lyndon L.; Ke, Pu Chun

2011-10-01

To delineate the complexity of the response of cells to nanoparticles we have performed a study on HT-29 human colon carcinoma cells exposed first to a fullerene derivative C60(OH)20 and then to physiological copper ions. Our cell viability, proliferation, and intracellular reactive oxygen species (ROS) production assays clearly indicated that C60(OH)20 suppressed cell damage as well as ROS production induced by copper, probably through neutralization of the metal ions by C60(OH)20 in the extracellular space, as well as by adsorption and uptake of the nanoparticles surface-modified by the biomolecular species in the cell medium. This double-exposure study provides new data on the effects of nanoparticles on cell metabolism and may aid the treatment of oxidant-mediated diseases using nanomedicine.

Dispersion strengthened copper

DOEpatents

Sheinberg, Haskell; Meek, Thomas T.; Blake, Rodger D.

1989-01-01

A composition of matter comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide, and a method for making this composition of matter.

Dispersion strengthened copper

DOEpatents

Sheinberg, Haskell; Meek, Thomas T.; Blake, Rodger D.

1990-01-01

A composition of matter comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide, and a method for making this composition of matter.

The cell labeling efficacy, cytotoxicity and relaxivity of copper-activated MRI/PET imaging contrast agents.

PubMed

Patel, Daksha; Kell, Arnold; Simard, Benoit; Xiang, Bo; Lin, Hung Yu; Tian, Ganghong

2011-02-01

A new class of nanoparticle-based dual-modality positron emission tomography/magnetic resonance imaging (PET/MRI) contrast agents has been developed. The probe consists of a superparamagnetic iron oxide (SPIO) or manganese oxide core coated with 3,4-dihydroxy-D,L-phenylalanine (DL-DOPA). The chelator 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) was conjugated to DOPA termini. The DOTA modified nanoparticles allow chelation of copper for PET imaging. These surface functionalized nanoparticle-based probes have been characterized by various analytical techniques. The cell-labeling efficacy, cytotoxicity and relaxivity of these nanoparticles have been evaluated and compared with the same properties of one of the most commonly utilized MRI contrast agents, Feridex(®). Evidently, this new nanoparticle has a great potential for use in cell tracking with MRI and PET in the absence of transfecting agent. It is noteworthy that there is a sharp increase in r(2) relaxivity of these nanoparticles on coordination with Cu(2+) ions. Thus these iron oxide nanoparticles can also be explored as the smart magnetic resonance (MR) sensor for the detection of micromolar changes in copper concentration for neurodegenerative diseases such as Alzheimer's disease, Menkes and Wilson's diseases, amyotrophic lateral sclerosis and prion diseases. Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.

Copper slag as a catalyst for mercury oxidation in coal combustion flue gas.

PubMed

Li, Hailong; Zhang, Weilin; Wang, Jun; Yang, Zequn; Li, Liqing; Shih, Kaimin

2018-04-01

Copper slag is a byproduct of the pyrometallurgical smelting of copper concentrate. It was used in this study to catalyze elemental mercury (Hg 0 ) oxidation in simulated coal combustion flue gas. The copper slag exhibited excellent catalytic performance in Hg 0 oxidation at temperatures between 200 °C and 300 °C. At the most optimal temperature of 250 °C, a Hg 0 oxidation efficiency of 93.8% was achieved under simulated coal combustion flue gas with both a high Hg 0 concentration and a high gas hourly space velocity of 128,000 h -1 . Hydrogen chloride (HCl) was the flue gas component responsible for Hg 0 oxidation over the copper slag. The transition metal oxides, including iron oxides and copper oxide in the copper slag, exhibited significant catalytic activities in the surface-mediated oxidation of Hg 0 in the presence of HCl. It is proposed that the Hg 0 oxidation over the copper slag followed the Langmuir-Hinshelwood mechanism whereby reactive chlorine species that originated from HCl reacted with the physically adsorbed Hg 0 to form oxidized mercury. This study demonstrated the possibility of reusing copper slag as a catalyst for Hg 0 oxidation and revealed the mechanisms involved in the process and the key factors in the performance. This knowledge has fundamental importance in simultaneously reducing industrial waste and controlling mercury emissions from coal-fired power plants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modified band alignment effect in ZnO/Cu2O heterojunction solar cells via Cs2O buffer insertion

NASA Astrophysics Data System (ADS)

Eom, Kiryung; Lee, Dongyoon; Kim, Seunghwan; Seo, Hyungtak

2018-02-01

The effects of a complex buffer layer of cesium oxide (Cs2O) on the photocurrent response in oxide heterojunction solar cells (HSCs) were investigated. A p-n junction oxide HSC was fabricated using p-type copper (I) oxide (Cu2O) and n-type zinc oxide (ZnO); the buffer layer was inserted between the Cu2O and fluorine-doped tin oxide (FTO). Ultraviolet-visible (UV-vis) and x-ray and ultraviolet photoelectron spectroscopy analyses were performed to characterize the electronic band structures of cells, both with and without this buffer layer. In conjunction with the measured band electronic structures, the significantly improved visible-range photocurrent spectra of the buffer-inserted HSC were analyzed in-depth. As a result, the 1 sun power conversion efficiency was increased by about three times by the insertion of buffer layer. The physicochemical origin of the photocurrent enhancement was mainly ascribed to the increased photocarrier density in the buffer layer and modified valence band offset to promote the effective hole transfer at the interface to FTO on the band-alignment model.

Electrochemical and spectroscopic effects of mixed substituents in bis(phenolate)–copper(II) galactose oxidase model complexes

PubMed Central

Pratt, Russell C.; Lyons, Christopher T.; Wasinger, Erik C.; Stack, T. Daniel. P.

2012-01-01

Non-symmetric substitution of salen (1R1,R2) and reduced salen (2R1,R2) CuII-phenoxyl complexes with a combination of -tBu, -SiPr, and -OMe substituents leads to dramatic differences in their redox and spectroscopic properties, providing insight into the influence of the cysteine-modified tyrosine cofactor in the enzyme galactose oxidase (GO). Using a modified Marcus-Hush analysis, the oxidized copper complexes are characterized as Class II mixed-valent due to the electronic differentiation between the two substituted phenolates. Sulfur K-edge X-ray absorption spectroscopy (XAS) assesses the degree of radical delocalization onto the single sulfur atom of non-symmetric [1tBu,SMe]+ at 7%, consistent with other spectroscopic and electrochemical results that suggest preferential oxidation of the -SMe bearing phenolate. Estimates of the thermodynamic free-energy difference between the two localized states (ΔG∘) and reorganizational energies (λR1R2) of [1R1,R2]+ and [2R1,R2]+ leads to accurate predictions of the spectroscopically observed IVCT transition energies. Application of the modified Marcus-Hush analysis to GO using parameters determined for [2R1,R2]+ predicts a νmax of ~ 13600 cm−1, well within the energy range of the broad Vis-NIR band displayed by the enzyme. PMID:22471355

Zeolite A functionalized with copper nanoparticles and graphene oxide for simultaneous electrochemical determination of dopamine and ascorbic acid.

PubMed

He, Ping; Wang, Wei; Du, Licheng; Dong, Faqin; Deng, Yuequan; Zhang, Tinghong

2012-08-20

A novel Cu-zeolite A/graphene modified glassy carbon electrode for the simultaneous electrochemical determination of dopamine (DA) and ascorbic acid (AA) has been described. The Cu-zeolite A/graphene composites were prepared using Cu(2+) functionalized zeolite A and graphene oxide as the precursor, and subsequently reduced by chemical agents. The composites were characterized by X-ray diffraction, Fourier transform infrared spectra and scanning electron microscopy. Based on the Cu-zeolite A/graphene-modified electrode, the potential difference between the oxidation peaks of DA and AA was over 200mV, which was adequate for the simultaneous electrochemical determination of DA and AA. Also the proposed Cu-zeolite/graphene-modified electrode showed higher electrocatalytic performance than zeolite/graphene electrode or graphene-modified electrode. The electrocatalytic oxidation currents of DA and AA were linearly related to the corresponding concentration in the range of 1.0×10(-7)-1.9×10(-5)M for DA and 2.0×10(-5)-2.0×10(-4)M for AA. Detection limits (S/N=3) were estimated to be 4.1×10(-8)M for DA and 1.1×10(-5)M for AA, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Effects of supplementation with two sources and two levels of copper on meat lipid oxidation, meat colour and superoxide dismutase and glutathione peroxidase enzyme activities in Nellore beef cattle.

PubMed

Correa, Lísia Bertonha; Zanetti, Marcus Antonio; Del Claro, Gustavo Ribeiro; de Paiva, Fernanda Alves; da Luz e Silva, Saulo; Netto, Arlindo Saran

2014-10-28

In the present study, thirty-five Nellore bulls were used to determine the effects of two levels and two sources (organic and inorganic) of Cu supplementation on the oxidative stability of lipids, measured by the thiobarbituric acid-reactive substance (TBARS) test, meat colour and superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px) enzyme activities. The following treatments were used: (1) control (C) - basal diet without supplementation of Cu (7 mg Cu/kg DM); (2) I10 - basal diet supplemented with 10 mg Cu/kg DM in the form of copper sulphate (inorganic form); (3) I40 - basal diet supplemented with 40 mg Cu/kg DM in the form of copper sulphate; (4) O10 - basal diet supplemented with 10 mg Cu/kg DM in the form of copper proteinate (organic form); (5) O40 - basal diet supplemented with 40 mg Cu/kg DM in the form of copper proteinate. Lipid oxidation was determined in meat samples exposed to display, modified atmosphere (MA) and vacuum packaging (VC) conditions and in liver samples using the TBARS test. These samples were also evaluated for meat discolouration after exposure to air. The activities of SOD and GSH-Px enzymes were determined in liver samples. In display, MA and VC conditions, the TBARS values of samples from animals supplemented with 40 mg Cu/kg DM were lower than those of samples from control animals. There was no effect of treatment on the colour variables (L*, a*, b*). There was also no significant effect of treatment on hepatic TBARS concentrations and GSH-Px activity. Supplementation with Cu at 40 mg/kg, regardless of the source, induced higher hepatic SOD activity compared with the control treatment. In conclusion, Cu supplementation improved the oxidative stability of lipids in samples exposed to display, MA and VC conditions, demonstrating the antioxidant effect of this mineral.

Oxidation Mechanism of Copper Selenide

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

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.

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

PubMed Central

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

2016-01-01

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

Green synthesis of colloidal copper oxide nanoparticles using Carica papaya and its application in photocatalytic dye degradation

NASA Astrophysics Data System (ADS)

Sankar, Renu; Manikandan, Perumal; Malarvizhi, Viswanathan; Fathima, Tajudeennasrin; Shivashangari, Kanchi Subramanian; Ravikumar, Vilwanathan

2014-03-01

Copper oxide (CuO) nanoparticles were synthesized by treating 5 mM cupric sulphate with Carica papaya leaves extract. The kinetics of the reaction was studied using UV-visible spectrophotometry. An intense surface Plasmon resonance between 250-300 nm in the UV-vis spectrum clearly reveals the formation of copper oxide nanoparticles. The results of scanning electron microscopy (SEM) and dynamic light scattering (DLS) exhibited that the green synthesized copper oxide nanoparticles are rod in shape and having a mean particle size of 140 nm, further negative zeta potential disclose its stability at -28.9 mV. The Fourier-transform infrared (FTIR) spectroscopy results examined the occurrence of bioactive functional groups required for the reduction of copper ions. X-ray diffraction (XRD) spectra confirmed the copper oxide nanoparticles crystalline nature. Furthermore, colloidal copper oxide nanoparticles effectively degrade the Coomassie brilliant blue R-250 dye beneath the sunlight.

Copper NPs decorated titania: A novel synthesis by high energy US with a study of the photocatalytic activity under visible light.

PubMed

Stucchi, Marta; Bianchi, Claudia L; Pirola, Carlo; Cerrato, Giuseppina; Morandi, Sara; Argirusis, Christos; Sourkouni, Georgia; Naldoni, Alberto; Capucci, Valentino

2016-07-01

The most important drawback of the use of TiO2 as photocatalyst is its lack of activity under visible light. To overcome this problem, the surface modification of commercial micro-sized TiO2 by means of high-energy ultrasound (US), employing CuCl2 as precursor molecule to obtain both metallic copper as well as copper oxides species at the TiO2 surface, is here. We have prepared samples with different copper content, in order to evaluate its impact on the photocatalytic performances of the semiconductor, and studied in particular the photodegradation in the gas phase of some volatile organic molecules (VOCs), namely acetone and acetaldehyde. We used a LED lamp in order to have only the contribution of the visible wavelengths to the TiO2 activation (typical LED lights have no emission in the UV region). We employed several techniques (i.e., HR-TEM, XRD, FT-IR and UV-Vis) in order to characterize the prepared samples, thus evidencing different sample morphologies as a function of the various copper content, with a coherent correlation between them and the photocatalytic results. Firstly, we demonstrated the possibility to use US to modify the TiO2, even when it is commercial and micro-sized as well; secondly, by avoiding completely the UV irradiation, we confirmed that pure TiO2 is not activated by visible light. On the other hand, we showed that copper metal and metal oxides nanoparticles strongly and positively affect its photocatalytic activity. Copyright © 2016 Elsevier B.V. All rights reserved.

Ferric Oxide Mediated Formation of PCDD/Fs from 2-Monochlorophenol

PubMed Central

Nganai, Shadrack; Lomnicki, Slawo; Dellinger, Barry

2012-01-01

The copper oxide, surface-mediated formation of polychlorinated dibenzop-dioxins and dibenzofurans (PCDD/F) from precursors such as chlorinated phenols is considered to be a major source of PCDD/F emissions from combustion sources. In spite of being present at 2–50x higher concentrations than copper oxide, virtually no studies of the iron oxide-mediated formation of PCDD/F have been reported in the literature. We have performed packed bed, flow reactor studies of the reaction of 50 ppm gas phase 2-monochlorophenol (2-MCP) over a surface of 5% iron oxide on silica over a temperature range of 200–500 °C. Dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), 4,6-dichlorodibenzofuran (4,6-DCDF), and dibenzofuran (DF) were formed in maximum yields of 0.1, 0.2, 0.3, and 0.4 %, respectively. The yield of PCDD/F over iron oxide peaked at temperatures 50–100 °C higher in temperature than over copper oxide. The maximum yields of DD, 1-MCDD and 4,6-DCDF were 2x and 5x higher over iron oxide, respectively, than over copper oxide, while DF was not observed at all for copper oxide. The resulting PCDD/PCDF ratio was 0.39 versus 1.2 observed for iron oxide and copper oxide, respectively, which is in agreement with PCDD to PCDF ratios in full-scale combustors that are typically ≪1. The combination of 2–50x higher concentrations of iron oxide than copper oxide in most full-scale combustors and 2.5x higher yields of PCDD/F observed in the laboratory, suggest that iron oxide may contribute as much as 5–125x more than copper oxide to the emissions of PCDD/F from full-scale combustors. PMID:19238966

Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

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

Jernigan, Glenn Geoffrey

1994-10-01

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu 2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu 2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/molmore » < Cu 2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N 2 and CO 2. At the end of each reaction, the catalyst was found to be Cu 2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.« less

Enhanced thermal diffusivity of copperbased composites using copper-RGO sheets

NASA Astrophysics Data System (ADS)

Kim, Sangwoo; Kwon, Hyouk-Chon; Lee, Dohyung; Lee, Hyo-Soo

2017-11-01

The synthesis of copper-reduced graphene oxide (RGO) sheets was investigated in order to control the agglutination of interfaces and develop a manufacturing process for copper-based composite materials based on spark plasma sintering. To this end, copper-GO (graphene oxide) composites were synthesized using a hydrothermal method, while the copper-reduced graphene oxide composites were made by hydrogen reduction. Graphene oxide-copper oxide was hydrothermally synthesized at 80 °C for 5 h, and then annealed at 800 °C for 5 h in argon and hydrazine rate 9:1 to obtain copper-RGO flakes. The morphology and structure of these copper-RGO sheets were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. After vibratory mixing of the synthesized copper-RGO composites (0-2 wt%) with copper powder, they were sintered at 600 °C for 5 min under100 MPa of pressure by spark plasma sintering process. The thermal diffusivity of the resulting sintered composite was characterized by the laser flash method at 150 °C.

Coupling catalytic hydrolysis and oxidation of HCN over HZSM-5 modified by metal (Fe,Cu) oxides

NASA Astrophysics Data System (ADS)

Hu, Yanan; Liu, Jiangping; Cheng, Jinhuan; Wang, Langlang; Tao, Lei; Wang, Qi; Wang, Xueqian; Ning, Ping

2018-01-01

In this work, a series of metal oxides (Fe,Cu) modified HZSM-5 catalysts were synthesized by incipient-wetness impregnation method and then characterized by XRD, N2 adsorption-desorption, H2-TPR, NH3-TPD, UV-vis, FT-IR and XPS measurements. The catalytic hydrolysis and oxidation behaviors toward HCN were investigated. The results indicated that the Fe-Cu/HZSM-5 catalysts exhibited more excellent performence on coupling catalytic hydrolysis and oxidation of HCN than HZSM-5, Fe/HZSM-5, Cu/HZSM-5, and both nearly 100% HCN conversion and 80% N2 selectivity were obtained at about 250 °C. The improved catalytic performance could be ascribed to the creation of highly dispersed iron and copper composites on the surface of the HZSM-5 support, the excellent redox and regulated acid properties of the active ingredients. Moreover, the highly N2 selectivity could be attributed to the good interaction between the Fe and Cu nanocomposites which was facilitated to the NH3-SCR (selective catalytic reduction of NO by NH3) reaction.

Plasmonic doped semiconductor nanocrystals: Properties, fabrication, applications and perspectives

NASA Astrophysics Data System (ADS)

Kriegel, Ilka; Scotognella, Francesco; Manna, Liberato

2017-02-01

Degenerately doped semiconductor nanocrystals (NCs) are of recent interest to the NC community due to their tunable localized surface plasmon resonances (LSPRs) in the near infrared (NIR). The high level of doping in such materials with carrier densities in the range of 1021cm-3 leads to degeneracy of the doping levels and intense plasmonic absorption in the NIR. The lower carrier density in degenerately doped semiconductor NCs compared to noble metals enables LSPR tuning over a wide spectral range, since even a minor change of the carrier density strongly affects the spectral position of the LSPR. Two classes of degenerate semiconductors are most relevant in this respect: impurity doped semiconductors, such as metal oxides, and vacancy doped semiconductors, such as copper chalcogenides. In the latter it is the density of copper vacancies that controls the carrier concentration, while in the former the introduction of impurity atoms adds carriers to the system. LSPR tuning in vacancy doped semiconductor NCs such as copper chalcogenides occurs by chemically controlling the copper vacancy density. This goes in hand with complex structural modifications of the copper chalcogenide crystal lattice. In contrast the LSPR of degenerately doped metal oxide NCs is modified by varying the doping concentration or by the choice of host and dopant atoms, but also through the addition of capacitive charge carriers to the conduction band of the metal oxide upon post-synthetic treatments, such as by electrochemical- or photodoping. The NIR LSPRs and the option of their spectral fine-tuning make accessible important new features, such as the controlled coupling of the LSPR to other physical signatures or the enhancement of optical signals in the NIR, sensing application by LSPR tracking, energy production from the NIR plasmon resonance or bio-medical applications in the biological window. In this review we highlight the recent advances in the synthesis of various different plasmonic semiconductor NCs with LSPRs covering the entire spectral range, from the mid- to the NIR. We focus on copper chalcogenide NCs and impurity doped metal oxide NCs as the most investigated alternatives to noble metals. We shed light on the structural changes upon LSPR tuning in vacancy doped copper chalcogenide NCs and deliver a picture for the fundamentally different mechanism of LSPR modification of impurity doped metal oxide NCs. We review on the peculiar optical properties of plasmonic degenerately doped NCs by highlighting the variety of different optical measurements and optical modeling approaches. These findings are merged in an exhaustive section on new and exciting applications based on the special characteristics that plasmonic semiconductor NCs bring along.

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.

The effect of copper on eumelanin photophysics and morphology

NASA Astrophysics Data System (ADS)

Birch, David J. S.; Sutter, Jens U.

2013-02-01

Despite being an important pigment in skin, hair, the eye and the brain, melanin remains one of the most enigmatic of pigments. Although the main constituents of melanin are known to be dihydroxyindoles, its photophysics is complex and its detailed structure remains unknown. In this work we have arrested prior to completion the usual synthesis of eumelanin formed via auto-oxidation of 3, 4-dihydroxy-L-phenylalanine (L-DOPA), by the addition of copper ions. Using fluorescence techniques we report how copper modifies the self assembly of eumelanin by reducing the time to the onset of aggregation at pH 10 and yet produces simplified photophysics in terms of a clearly-defined fluorescence spectrum and a fluorescence decay that is described well by a dominant single lifetime of ~ 6ns. This behavior is consistent with copper inducing an enhanced abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). Metal ion binding to melanin is of particular importance to neurology and has potential applications in optoelectronics.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

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.

Industrial Tests to Modify Molten Copper Slag for Improvement of Copper Recovery

NASA Astrophysics Data System (ADS)

Guo, Zhengqi; Zhu, Deqing; Pan, Jian; Zhang, Feng; Yang, Congcong

2018-04-01

In this article, to improve the recovery of copper from copper slag by flotation process, industrial tests of the modification process involving addition of a composite additive into molten copper slag were conducted, and the modified slag was subjected to the flotation process to confirm the modification effect. The phase evolution of the slag in the modification process was revealed by thermodynamic calculations, x-ray diffraction, optical microscopy and scanning electron microscopy. The results show that more copper was transformed and enriched in copper sulfide phases. The magnetite content in the modified slag decreased, and that of "FeO" increased correspondingly, leading to a better fluidity of the molten slag, which improved the aggregation and growth of fine particles of the copper sulfide minerals. Closed-circuit flotation tests of the original and modified slags were conducted, and the results show that the copper recovery increased obviously from 69.15% to 73.38%, and the copper grade of concentrates was elevated slightly from 20.24% to 21.69%, further confirming that the industrial tests of the modification process were successful. Hence, the modification process has a bright future in industrial applications for enhancing the recovery of copper from the copper slag.

Solvent polarity effect on quality of n-octadecanethiol self-assembled monolayers on copper and oxidized copper

NASA Astrophysics Data System (ADS)

Zhang, Yaozhong; Zhou, Jun; Zhang, Xiaoli; Hu, Jun; Gao, Han

2014-11-01

This article reports the effect of solvent polarity on the formation of n-octadecanethiol self-assembled monolayers (C18SH-SAMs) on pure copper surface and oxidized copper surface. The quality of SAMs prepared in different solvents (n-hexane, toluene, trichloroethylene, chloroform, acetone, acetonitrile, ethanol) was monitored by EIS, RAIRS and XPS. The results indicated that C18SH-SAMs formed in these solvents were in good barrier properties on pure copper surface and the structures of monolayers formed in high polarity solvents were more compact and orderly than that formed in low polarity solvents. For comparison, C18SH adsorbed on the surface of oxidized copper in these solvents were studied and the results indicated that C18SH could be adsorbed on oxidized copper surface after the reduction of copper oxide layer by thiols. Compared with high polarity solvents, a limited reduction process of oxidized copper by thiols led to the incompletely formation of monolayers in low polarity solvents. This can be interpreted that the generated water on solid-liquid interface and a smaller reaction force restrict the continuous reduction reaction in low polarity solvents

Shape-dependent bactericidal activity of copper oxide nanoparticle mediated by DNA and membrane damage

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

Laha, Dipranjan; Pramanik, Arindam; Laskar, Aparna

Highlights: • Spherical and sheet shaped copper oxide nanoparticles were synthesized. • Physical characterizations of these nanoparticles were done by TEM, DLS, XRD, FTIR. • They showed shape dependent antibacterial activity on different bacterial strain. • They induced both membrane damage and ROS mediated DNA damage in bacteria. - Abstract: In this work, we synthesized spherical and sheet shaped copper oxide nanoparticles and their physical characterizations were done by the X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering. The antibacterial activity of these nanoparticles was determined on both gram positive and gram negative bacterial. Sphericalmore » shaped copper oxide nanoparticles showed more antibacterial property on gram positive bacteria where as sheet shaped copper oxide nanoparticles are more active on gram negative bacteria. We also demonstrated that copper oxide nanoparticles produced reactive oxygen species in both gram negative and gram positive bacteria. Furthermore, they induced membrane damage as determined by atomic force microscopy and scanning electron microscopy. Thus production of and membrane damage are major mechanisms of the bactericidal activity of these copper oxide nanoparticles. Finally it was concluded that antibacterial activity of nanoparticles depend on physicochemical properties of copper oxide nanoparticles and bacterial strain.« less

Copper crystallite in carbon molecular sieves for selective oxygen removal

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor); Seshan, Panchalam K. (Inventor)

1993-01-01

Carbon molecular sieves modified by the incorporation of finely divided elemental copper useful for the selective sorption of oxygen at elevated temperatures. The carbon molecular sieves can be regenerated by reduction with hydrogen. The copper modified carbon molecular sieves are prepared by pyrolysis of a mixture of a copper-containing material and polyfurfuryl alcohol to form a sorbent precursor. The sorbent precursors are then heated and reduced to produce copper modified carbon molecular sieves. The copper modified carbon molecular sieves are useful for sorption of all concentrations of oxygen at temperatures up to about 200.degree. C. They are also useful for removal of trace amount of oxygen from gases at temperatures up to about 600.degree. C.

Placental oxidative stress and decreased global DNA methylation are corrected by copper in the Cohen diabetic rat

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

Ergaz, Zivanit, E-mail: zivanit@hadassah.org.il; Guillemin, Claire; Neeman-azulay, Meytal

Fetal Growth Restriction (FGR) is a leading cause for long term morbidity. The Cohen diabetic sensitive rats (CDs), originating from Wistar, develop overt diabetes when fed high sucrose low copper diet (HSD) while the original outbred Sabra strain do not. HSD induced FGR and fetal oxidative stress, more prominent in the CDs, that was alleviated more effectively by copper than by the anti-oxidant vitamins C and E. Our aim was to evaluate the impact of copper or the anti-oxidant Tempol on placental size, protein content, oxidative stress, apoptosis and total DNA methylation. Animals were mated following one month of HSDmore » or regular chow diet and supplemented throughout pregnancy with either 0, 1 or 2 ppm of copper sulfate or Tempol in their drinking water. Placental weight on the 21st day of pregnancy decreased in dams fed HSD and improved upon copper supplementation. Placental/fetal weight ratio increased among the CDs. Protein content decreased in Sabra but increased in CDs fed HSD. Oxidative stress biochemical markers improved upon copper supplementation; immunohistochemistry for oxidative stress markers was similar between strains and diets. Caspase 3 was positive in more placentae of dams fed HSD than those fed RD. Placental global DNA methylation was decreased only among the CDs dams fed HSD. We conclude that FGR in this model is associated with smaller placentae, reduced DNA placental methylation, and increased oxidative stress that normalized with copper supplementation. DNA hypomethylation makes our model a unique method for investigating genes associated with growth, oxidative stress, hypoxia and copper. - Highlights: • Sensitive Cohen diabetic rats (CDs) had small placentae and growth restricted fetuses. • CDs dams fed high sucrose low copper diet had placental global DNA hypomethylation. • Caspase 3 was positive in more placentae of dams fed HSD than those fed RD. • Oxidative stress parameters improved by Tempol and resolved by copper supplementation. • Global DNA hypomethylation was resolved both by Tempol and by copper supplementation. • Placental oxidative stress parameters coincides previous findings in the fetal liver.« less

Green synthesis of colloidal copper oxide nanoparticles using Carica papaya and its application in photocatalytic dye degradation.

PubMed

Sankar, Renu; Manikandan, Perumal; Malarvizhi, Viswanathan; Fathima, Tajudeennasrin; Shivashangari, Kanchi Subramanian; Ravikumar, Vilwanathan

2014-01-01

Copper oxide (CuO) nanoparticles were synthesized by treating 5 mM cupric sulphate with Carica papaya leaves extract. The kinetics of the reaction was studied using UV-visible spectrophotometry. An intense surface Plasmon resonance between 250-300 nm in the UV-vis spectrum clearly reveals the formation of copper oxide nanoparticles. The results of scanning electron microscopy (SEM) and dynamic light scattering (DLS) exhibited that the green synthesized copper oxide nanoparticles are rod in shape and having a mean particle size of 140 nm, further negative zeta potential disclose its stability at -28.9 mV. The Fourier-transform infrared (FTIR) spectroscopy results examined the occurrence of bioactive functional groups required for the reduction of copper ions. X-ray diffraction (XRD) spectra confirmed the copper oxide nanoparticles crystalline nature. Furthermore, colloidal copper oxide nanoparticles effectively degrade the Coomassie brilliant blue R-250 dye beneath the sunlight. Copyright © 2013 Elsevier B.V. All rights reserved.

Improvement of the photovoltaic parameters of perovskite solar cells using a reduced-graphene-oxide-modified titania layer and soluble copper phthalocyanine as a hole transporter.

PubMed

Nouri, Esmaiel; Mohammadi, Mohammad Reza; Xu, Zong-Xiang; Dracopoulos, Vassilios; Lianos, Panagiotis

2018-01-24

Functional perovskite solar cells can be made by using a simple, inexpensive and stable soluble tetra-n-butyl-substituted copper phthalocyanine (CuBuPc) as a hole transporter. In the present study, TiO 2 /reduced graphene oxide (T/RGO) hybrids were synthesized via an in situ solvothermal process and used as electron acceptor/transport mediators in mesoscopic perovskite solar cells based on soluble CuBuPc as a hole transporter and on graphene oxide (GO) as a buffer layer. The impact of the RGO content on the optoelectronic properties of T/RGO hybrids and on the solar cell performance was studied, suggesting improved electron transport characteristics and photovoltaic parameters. An enhanced electron lifetime and recombination resistance led to an increase in the short circuit current density, open circuit voltage and fill factor. The device based on a T/RGO mesoporous layer with an optimal RGO content of 0.2 wt% showed 22% higher photoconversion efficiency and higher stability compared with pristine TiO 2 -based devices.

Laser-Induced, Local Oxidation of Copper Nanoparticle Films During Raman Measurements

NASA Astrophysics Data System (ADS)

Hight Walker, Angela R.; Cheng, Guangjun; Calizo, Irene

2011-03-01

The optical properties of gold and silver nanoparticles and their films have been thoroughly investigated as surface enhanced Raman scattering (SERS) substrates and chemical reaction promoters. Similar to gold and silver nanoparticles, copper nanoparticles exhibit distinct plasmon absorptions in the visible region. The work on copper nanoparticles and their films is limited due to their oxidization in air. However, their high reactivity actually provides an opportunity to exploit the laser-induced thermal effect and chemical reactions of these nanoparticles. Here, we present our investigation of the local oxidation of a copper nanoparticle film induced by a visible laser source during Raman spectroscopic measurements. The copper nanoparticle film is prepared by drop-casting chemically synthesized copper colloid onto silicon oxide/silicon substrate. The local oxidation induced by visible lasers in Raman spectroscopy is monitored with the distinct scattering peaks for copper oxides. Optical microscopy and scanning electron microscopy have been used to characterize the laser-induced morphological changes in the film. The results of this oxidation process with different excitation wavelengths and different laser powers will be presented.

Stabilization of Oxidized Copper Nanoclusters in Confined Spaces

DOE PAGES

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang; ...

2018-01-04

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

Oxidation-assisted graphene heteroepitaxy on copper foil.

PubMed

Reckinger, Nicolas; Tang, Xiaohui; Joucken, Frédéric; Lajaunie, Luc; Arenal, Raul; Dubois, Emmanuel; Hackens, Benoît; Henrard, Luc; Colomer, Jean-François

2016-11-10

We propose an innovative, easy-to-implement approach to synthesize aligned large-area single-crystalline graphene flakes by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.

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

Sarwar, Tarique; Zafaryab, Md; Husain, Mohammed Amir

Ferulic acid (FA) is a plant polyphenol showing diverse therapeutic effects against cancer, diabetes, cardiovascular and neurodegenerative diseases. FA is a known antioxidant at lower concentrations, however at higher concentrations or in the presence of metal ions such as copper, it may act as a pro-oxidant. It has been reported that copper levels are significantly raised in different malignancies. Cancer cells are under increased oxidative stress as compared to normal cells. Certain therapeutic substances like polyphenols can further increase this oxidative stress and kill cancer cells without affecting the proliferation of normal cells. Through various in vitro experiments we havemore » shown that the pro-oxidant properties of FA are enhanced in the presence of copper. Comet assay demonstrated the ability of FA to cause oxidative DNA breakage in human peripheral lymphocytes which was ameliorated by specific copper-chelating agent such as neocuproine and scavengers of ROS. This suggested the mobilization of endogenous copper in ROS generation and consequent DNA damage. These results were further validated through cytotoxicity experiments involving different cell lines. Thus, we conclude that such a pro-oxidant mechanism involving endogenous copper better explains the anticancer activities of FA. This would be an alternate non-enzymatic, and copper-mediated pathway for the cytotoxic activities of FA where it can selectively target cancer cells with elevated levels of copper and ROS. - Highlights: • Pro-oxidant properties of ferulic acid are enhanced in presence of copper. • Ferulic acid causes oxidative DNA damage in lymphocytes as observed by comet assay. • DNA damage was ameliorated by copper chelating agent neocuproine and ROS scavengers. • Endogenous copper is involved in ROS generation causing DNA damage. • Ferulic acid exerts cancer cell specific cytotoxicity as observed by MTT assay.« less

Biosynthesis and characterization of Acalypha indica mediated copper oxide nanoparticles and evaluation of its antimicrobial and anticancer activity.

PubMed

Sivaraj, Rajeshwari; Rahman, Pattanathu K S M; Rajiv, P; Narendhran, S; Venckatesh, R

2014-08-14

Copper oxide nanoparticles were synthesized by biological method using aqueous extract of Acalypha indica leaf and characterized by UV-visible spectroscopy, XRD, FT-IR, SEM TEM and EDX analysis. The synthesised particles were highly stable, spherical and particle size was in the range of 26-30 nm. The antimicrobial activity of A.indica mediated copper oxide nanoparticles was tested against selected pathogens. Copper oxide nanoparticles showed efficient antibacterial and antifungal effect against Escherichia coli, Pseudomonas fluorescens and Candida albicans. The cytotoxicity activity of A.indica mediated copper nanoparticles was evaluated by MTT assay against MCF-7 breast cancer cell lines and confirmed that copper oxide nanoparticles have cytotoxicity activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Dispersion strengthened copper

DOEpatents

Sheinberg, H.; Meek, T.T.; Blake, R.D.

1990-01-09

A composition of matter is described which is comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide. A method for making this composition of matter is also described. This invention relates to the art of powder metallurgy and, more particularly, it relates to dispersion strengthened metals.

Microfluidic Encapsulation of Prickly Zinc-Doped Copper Oxide Nanoparticles with VD1142 Modified Spermine Acetalated Dextran for Efficient Cancer Therapy.

PubMed

Zhang, Hongbo; Liu, Dongfei; Wang, Liang; Liu, Zehua; Wu, Runrun; Janoniene, Agne; Ma, Ming; Pan, Guoqing; Baranauskiene, Lina; Zhang, Linlin; Cui, Wenguo; Petrikaite, Vilma; Matulis, Daumantas; Zhao, Hongxia; Pan, Jianming; Santos, Hélder A

2017-06-01

Structural features of nanoparticles have recently been explored for different types of applications. To explore specific particles as nanomedicine and physically destroy cancer is interesting, which might avoid many obstacles in cancer treatment, for example, drug resistance. However, one key element and technical challenge of those systems is to selectively target them to cancer cells. As a proof-of-concept, Prickly zinc-doped copper oxide (Zn-CuO) nanoparticles (Prickly NPs) have been synthesized, and subsequently encapsulated in a pH-responsive polymer; and the surface has been modified with a novel synthesized ligand, 3-(cyclooctylamino)-2,5,6-trifluoro-4-[(2-hydroxyethyl)sulfonyl] benzenesulfonamide (VD1142). The Prickly NPs exhibit very effective cancer cell antiproliferative capability. Moreover, the polymer encapsulation shields the Prickly NPs from unspecific nanopiercing and, most importantly, VD1142 endows the engineered NPs to specifically target to the carbonic anhydrase IX, a transmembrane protein overexpressed in a wide variety of cancer tumors. Intracellularly, the Prickly NPs disintegrate into small pieces that upon endosomal escape cause severe damage to the endoplasmic reticulum and mitochondria of the cells. The engineered Prickly NP is promising in efficient and targeted cancer treatment and it opens new avenue in nanomedication. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring of trace amounts of heavy metals in different food and water samples by flame atomic absorption spectrophotometer after preconcentration by amine-functionalized graphene nanosheet.

PubMed

Behbahani, Mohammad; Tapeh, Nasim Akbari Ghareh; Mahyari, Mojtaba; Pourali, Ali Reza; Amin, Bahareh Golrokh; Shaabani, Ahmad

2014-11-01

We are introducing graphene oxide modified with amine groups as a new solid phase for extraction of heavy metal ions including cadmium(II), copper(II), nickel(II), zinc(II), and lead(II). Effects of pH value, flow rates, type, concentration, and volume of the eluent, breakthrough volume, and the effect of potentially interfering ions were studied. Under optimized conditions, the extraction efficiency is >97 %, the limit of detections are 0.03, 0.05, 0.2, 0.1, and 1 μg L(-1) for the ions of cadmium, copper, nickel, zinc, and lead, respectively, and the adsorption capacities for these ions are 178, 142, 110, 125, and 210 mg g(-1). The amino-functionalized graphene oxide was characterized by thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, and Fourier transform infrared spectrometry. The proposed method was successfully applied in the analysis of environmental water and food samples. Good spiked recoveries over the range of 95.8-100.0 % were obtained. This work not only proposes a useful method for sample preconcentration but also reveals the great potential of modified graphene as an excellent sorbent material in analytical processes.

Heat transfer from an oxidized large copper surface to liquid helium: Dependence on surface orientation and treatment

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

Iwamoto, A.; Mito, T.; Takahata, K.

Heat transfer of large copper plates (18 x 76 mm) in liquid helium has been measured as a function of orientation and treatment of the heat transfer surface. The results relate to applications of large scale superconductors. In order to clarify the influence of the area where the surface treatment peels off, the authors studied five types of heat transfer surface areas including: (a) 100% polished copper sample, (b) and (c) two 50% oxidized copper samples having different patterns of oxidation, (d) 75% oxidized copper sample, (e) 90% oxidized copper sample, and (f) 100% oxidized copper sample. They observed thatmore » the critical heat flux depends on the heat transfer surface orientation. The critical heat flux is a maximum at angles of 0{degrees} - 30{degrees} and decreases monotonically with increasing angles above 30{degrees}, where the angle is taken in reference to the horizontal axis. On the other hand, the minimum heat flux is less dependent on the surface orientation. More than 75% oxidation on the surface makes the critical heat flux increase. The minimum heat fluxes of the 50 and 90% oxidized Cu samples approximately agree with that of the 100% oxidized Cu sample. Experiments and calculations show that the critical and the minimum heat fluxes are a bilinear function of the fraction of oxidized surface area.« less

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

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

Zhang, Peili; Li, Lin; Nordlund, Dennis

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE PAGES

Zhang, Peili; Li, Lin; Nordlund, Dennis; ...

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Control of the Structure of Diffusion Layer in Carbon Steels Under Nitriding with Preliminary Deposition of Copper Oxide Catalytic Films

NASA Astrophysics Data System (ADS)

Petrova, L. G.; Aleksandrov, V. A.; Malakhov, A. Yu.

2017-07-01

The effect of thin films of copper oxide deposited before nitriding on the phase composition and the kinetics of growth of diffusion layers in carbon steels is considered. The process of formation of an oxide film involves chemical reduction of pure copper on the surface of steel specimens from a salt solution and subsequent oxidation under air heating. The oxide film exerts a catalytic action in nitriding of low- and medium-carbon steels, which consists in accelerated growth of the diffusion layer, the nitride zone in the first turn. The kinetics of the nitriding process and the phase composition of the layer are controlled by the thickness of the copper oxide precursor, i.e., the deposited copper film.

Modeling the ignition of a copper oxide aluminum thermite

NASA Astrophysics Data System (ADS)

Lee, Kibaek; Stewart, D. Scott; Clemenson, Michael; Glumac, Nick; Murzyn, Christopher

2017-01-01

An experimental "striker confinement" shock compression experiment was developed in the Glumac-group at the University of Illinois to study ignition and reaction in composite reactive materials. These include thermitic and intermetallic reactive powders. Sample of materials such as a thermite mixture of copper oxide and aluminum powders are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into the reactive material and the resulting compression causes shock compaction of the material and rapid heating. At that point one observes significant reaction and propagation of fronts. But the fronts are peculiar in that they are comprised of reactive events that can be traced to the reaction of the initially separated reactants of copper oxide and aluminum that react at their mutual interfaces, that nominally make copper liquid and aluminum oxide products. We discuss our model of the ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model [1], that includes multi-components for liquid and solid phases of aluminum, copper oxide, copper and aluminum oxide, can predict the events observed at the particle scale in the experiments.

Process for removing copper in a recoverable form from solid scrap metal

DOEpatents

Hartman, Alan D.; Oden, Laurance L.; White, Jack C.

1995-01-01

A process for removing copper in a recoverable form from a copper/solid ferrous scrap metal mix is disclosed. The process begins by placing a copper/solid ferrous scrap metal mix into a reactor vessel. The atmosphere within the reactor vessel is purged with an inert gas or oxidizing while the reactor vessel is heated in the area of the copper/solid ferrous scrap metal mix to raise the temperature within the reactor vessel to a selected elevated temperature. Air is introduced into the reactor vessel and thereafter hydrogen chloride is introduced into the reactor vessel to obtain a desired air-hydrogen chloride mix. The air-hydrogen chloride mix is operable to form an oxidizing and chloridizing atmosphere which provides a protective oxide coating on the surface of the solid ferrous scrap metal in the mix and simultaneously oxidizes/chloridizes the copper in the mix to convert the copper to a copper monochloride gas for transport away from the solid ferrous scrap metal. After the copper is completely removed from the copper/solid ferrous scrap metal mix, the flows of air and hydrogen chloride are stopped and the copper monochloride gas is collected for conversion to a recoverable copper species.

Glucose sensing on graphite screen-printed electrode modified by sparking of copper nickel alloys.

PubMed

Riman, Daniel; Spyrou, Konstantinos; Karantzalis, Alexandros E; Hrbac, Jan; Prodromidis, Mamas I

2017-04-01

Electric spark discharge was employed as a green, fast and extremely facile method to modify disposable graphite screen-printed electrodes (SPEs) with copper, nickel and mixed copper/nickel nanoparticles (NPs) in order to be used as nonenzymatic glucose sensors. Direct SPEs-to-metal (copper, nickel or copper/nickel alloys with 25/75, 50/50 and 75/25wt% compositions) sparking at 1.2kV was conducted in the absence of any solutions under ambient conditions. Morphological characterization of the sparked surfaces was performed by scanning electron microscopy, while the chemical composition of the sparked NPs was evaluated with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The performance of the various sparked SPEs towards the electro oxidation of glucose in alkaline media and the critical role of hydroxyl ions were evaluated with cyclic voltammetry and kinetic studies. Results indicated a mixed charge transfer- and hyroxyl ion transport-limited process. Best performing sensors fabricated by Cu/Ni 50/50wt% alloy showed linear response over the concentration range 2-400μM glucose and they were successfully applied to the amperometric determination of glucose in blood. The detection limit (S/N 3) and the relative standard deviation of the method were 0.6µM and <6% (n=5, 2µM glucose), respectively. Newly devised sparked Cu/Ni graphite SPEs enable glucose sensing with distinct advantages over existing glucose chemical sensors in terms of cost, fabrication simplicity, disposability, and adaptation of green methods in sensor's development. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel highly selective and sensitive detection of serotonin based on Ag/polypyrrole/Cu2O nanocomposite modified glassy carbon electrode.

PubMed

Selvarajan, S; Suganthi, A; Rajarajan, M

2018-06-01

A silver/polypyrrole/copper oxide (Ag/PPy/Cu 2 O) ternary nanocomposite was prepared by sonochemical and oxidative polymerization simple way, in which Cu 2 O was decorated with Ag nanoparticles, and covered by polyprrole (PPy) layer. The as prepared materials was characterized by UV-vis-spectroscopy (UV-vis), FT-IR, X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM) with EDX, high resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). Sensing of serotonin (5HT) was evaluated electrocatalyst using polypyrrole/glassy carbon electrode (PPy/GCE), polypyrrole/copper oxide/glassy carbon electrode (PPy/Cu 2 O/GCE) and silver/polypyrrole/copper oxide/glassy carbon electrode (Ag/PPy/Cu 2 O/GCE). The Ag/PPy/Cu 2 O/GCE was electrochemically treated in 0.1MPBS solution through cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The peak current response increases linearly with 5-HT concentration from 0.01 to 250 µmol L -1 and the detection limit was found to be 0.0124 μmol L -1 . It exhibits high electrocatalytic activity, satisfactory repeatability, stability, fast response and good selectivity against potentially interfering species, which suggests its potential in the development of sensitive, selective, easy-operation and low-cost serotonin sensor for practical routine analyses. The proposed method is potential to expand the possible applied range of the nanocomposite material for detection of various concerned electro active substances. Copyright © 2018 Elsevier B.V. All rights reserved.

Absorptive coating for aluminum solar panels

NASA Technical Reports Server (NTRS)

Desmet, D.; Jason, A.; Parr, A.

1979-01-01

Method for coating forming coating of copper oxide from copper component of sheet aluminum/copper alloy provides strong durable solar heat collector panels. Copper oxide coating has solar absorption characteristics similar to black chrome and is much simpler and less costly to produce.

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

NASA Astrophysics Data System (ADS)

Wang, Zicheng; Wei, Renbo; Liu, Xiaobo

2017-01-01

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

Analytical Transmission Electron Microscopy Studies on Copper-Alumina Interfaces.

DTIC Science & Technology

1999-06-01

association with alumina, such as, copper, aluminum, chromium, silver, and gold . In particular, copper has been chosen because of its excellent...similar results in variance. However, the oxide calculation program assumes that all elements are 100% oxidized with no monoatomic species or mixed oxide

Evaluation of antioxidant and anticancer activity of copper oxide nanoparticles synthesized using medicinally important plant extracts.

PubMed

Rehana, Dilaveez; Mahendiran, D; Kumar, R Senthil; Rahiman, A Kalilur

2017-05-01

Copper oxide (CuO) nanoparticles were synthesized by green chemistry approach using different plant extracts obtained from the leaves of Azadirachta indica, Hibiscus rosa-sinensis, Murraya koenigii, Moringa oleifera and Tamarindus indica. In order to compare their efficiency, the same copper oxide nanoparticles was also synthesized by chemical method. Phytochemical screening of the leaf extracts showed the presence of carbohydrates, flavonoids, glycosides, phenolic compounds, saponins, tannins, proteins and amino acids. FT IR spectra confirmed the possible biomolecules responsible for the formation of copper oxide nanoparticles. The surface plasmon resonance absorption band at 220-235nm in the UV-vis spectra also supports the formation of copper oxide nanoparticles. XRD patterns revealed the monoclinic phase of the synthesized copper oxide nanoparticles. The average size, shape and the crystalline nature of the nanoparticles were determined by SEM, TEM and SAED analysis. EDX analysis confirmed the presence of elements in the synthesized nanoparticles. The antioxidant activity was evaluated by three different free radical scavenging assays. The cytotoxicity of copper oxide nanoparticles was evaluated against four cancer cell lines such as human breast (MCF-7), cervical (HeLa), epithelioma (Hep-2) and lung (A549), and one normal human dermal fibroblast (NHDF) cell line. The morphological changes were evaluated using Hoechst 33258 staining assay. Copper oxide nanoparticles synthesized by green method exhibited high antioxidant and cytotoxicity than that synthesized by chemical method. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Macroscopic Streamer Growths in Acidic, Metal-Rich Mine Waters in North Wales Consist of Novel and Remarkably Simple Bacterial Communities

PubMed Central

Hallberg, Kevin B.; Coupland, Kris; Kimura, Sakurako; Johnson, D. Barrie

2006-01-01

The microbial composition of acid streamers (macroscopic biofilms) in acidic, metal-rich waters in two locations (an abandoned copper mine and a chalybeate spa) in north Wales was studied using cultivation-based and biomolecular techniques. Known chemolithotrophic and heterotrophic acidophiles were readily isolated from disrupted streamers, but they accounted for only <1 to 7% of the total microorganisms present. Fluorescent in situ hybridization (FISH) revealed that 80 to 90% of the microbes in both types of streamers were β-Proteobacteria. Terminal restriction fragment length polymorphism analysis of the streamers suggested that a single bacterial species was dominant in the copper mine streamers, while two distinct bacteria (one of which was identical to the bacterium found in the copper mine streamers) accounted for about 90% of the streamers in the spa water. 16S rRNA gene clone libraries showed that the β-proteobacterium found in both locations was closely related to a clone detected previously in acid mine drainage in California and that its closest characterized relatives were neutrophilic ammonium oxidizers. Using a modified isolation technique, this bacterium was isolated from the copper mine streamers and shown to be a novel acidophilic autotrophic iron oxidizer. The β-proteobacterium found only in the spa streamers was closely related to the neutrophilic iron oxidizer Gallionella ferruginea. FISH analysis using oligonucleotide probes that targeted the two β-proteobacteria confirmed that the biodiversity of the streamers in both locations was very limited. The microbial compositions of the acid streamers found at the two north Wales sites are very different from the microbial compositions of the previously described acid streamers found at Iron Mountain, California, and the Rio Tinto, Spain. PMID:16517651

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.

Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural with ALD overcoating (II) – Comparison between TiO2 and Al2O3 overcoatings

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

Zhang, Hongbo; Canlas, Christian; Kropf, A. Jeremy

2015-01-01

TiO2 atomic layer deposition (ALD) overcoatings were applied to copper chromite catalysts to increase the stability for 2-furfuraldehyde (“furfural”) hydrogenation. After overcoating, about 75% activity was preserved compared to neat copper chromite: much higher activity than an alumina ALD overcoated catalyst with a similar number of ALD cycles. The effects of ALD TiO2 on the active Cu nanoparticles were studied extensively using both in-situ TPR/isothermal-oxidation and in-situ furfural hydrogenation via Cu XAFS. The redox properties of Cu were modified only slightly by the TiO2 ALD overcoat. However, a subtle electronic interaction was observed between the TiO2 ALD layers and themore » Cu nanoparticles. With calcination at 500 °C the interaction between the TiO2 overcoat and the underlying catalyst is strong enough to inhibit migration and site blocking by chromite, but is sufficiently weaker than the interaction between the Al2O3 overcoat and copper chromite that it does not strongly inhibit the catalytic activity of the copper nanoparticles.« less

Intracellular Copper Does Not Catalyze the Formation of Oxidative DNA Damage in Escherichia coli▿

PubMed Central

Macomber, Lee; Rensing, Christopher; Imlay, James A.

2007-01-01

Because copper catalyzes the conversion of H2O2 to hydroxyl radicals in vitro, it has been proposed that oxidative DNA damage may be an important component of copper toxicity. Elimination of the copper export genes, copA, cueO, and cusCFBA, rendered Escherichia coli sensitive to growth inhibition by copper and provided forcing circumstances in which this hypothesis could be tested. When the cells were grown in medium supplemented with copper, the intracellular copper content increased 20-fold. However, the copper-loaded mutants were actually less sensitive to killing by H2O2 than cells grown without copper supplementation. The kinetics of cell death showed that excessive intracellular copper eliminated iron-mediated oxidative killing without contributing a copper-mediated component. Measurements of mutagenesis and quantitative PCR analysis confirmed that copper decreased the rate at which H2O2 damaged DNA. Electron paramagnetic resonance (EPR) spin trapping showed that the copper-dependent H2O2 resistance was not caused by inhibition of the Fenton reaction, for copper-supplemented cells exhibited substantial hydroxyl radical formation. However, copper EPR spectroscopy suggested that the majority of H2O2-oxidizable copper is located in the periplasm; therefore, most of the copper-mediated hydroxyl radical formation occurs in this compartment and away from the DNA. Indeed, while E. coli responds to H2O2 stress by inducing iron sequestration proteins, H2O2-stressed cells do not induce proteins that control copper levels. These observations do not explain how copper suppresses iron-mediated damage. However, it is clear that copper does not catalyze significant oxidative DNA damage in vivo; therefore, copper toxicity must occur by a different mechanism. PMID:17189367

Copper induces hepatocyte injury due to the endoplasmic reticulum stress in cultured cells and patients with Wilson disease

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

Oe, Shinji, E-mail: ooes@med.uoeh-u.ac.jp; Miyagawa, Koichiro, E-mail: koichiro@med.uoeh-u.ac.jp; Honma, Yuichi, E-mail: y-homma@med.uoeh-u.ac.jp

Copper is an essential trace element, however, excess copper is harmful to human health. Excess copper-derived oxidants contribute to the progression of Wilson disease, and oxidative stress induces accumulation of abnormal proteins. It is known that the endoplasmic reticulum (ER) plays an important role in proper protein folding, and that accumulation of misfolded proteins disturbs ER homeostasis resulting in ER stress. However, copper-induced ER homeostasis disturbance has not been fully clarified. We treated human hepatoma cell line (Huh7) and immortalized-human hepatocyte cell line (OUMS29) with copper and chemical chaperones, including 4-phenylbutyrate and ursodeoxycholic acid. We examined copper-induced oxidative stress, ERmore » stress and apoptosis by immunofluorescence microscopy and immunoblot analyses. Furthermore, we examined the effects of copper on carcinogenesis. Excess copper induced not only oxidative stress but also ER stress. Furthermore, excess copper induced DNA damage and reduced cell proliferation. Chemical chaperones reduced this copper-induced hepatotoxicity. Excess copper induced hepatotoxicity via ER stress. We also confirmed the abnormality of ultra-structure of the ER of hepatocytes in patients with Wilson disease. These findings show that ER stress plays a pivotal role in Wilson disease, and suggests that chemical chaperones may have beneficial effects in the treatment of Wilson disease.« less

Modeling the Shock Ignition of a Copper Oxide Aluminum Thermite

NASA Astrophysics Data System (ADS)

Lee, Kibaek; Stewart, D. Scott; Clemenson, Michael; Glumac, Nick; Murzyn, Christopher

2015-06-01

An experimental ``striker confinement'' shock compression test was developed in the Glumac-group at the University of Illinois to study ignition and reaction in composite reactive materials. These include thermitic and intermetallic reactive powders. The test places a sample of materials such as a thermite mixture of copper oxide and aluminum powders that are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into reactive material and the resulting compression causes shock compaction of the material and rapid heating. At that point one observes significant reaction and propagation of fronts. But the fronts are peculiar in that they are comprised of reactive events that can be traced to the reaction/diffusion of the initially separated reactants of copper oxide and aluminum that react at their mutual interfaces that nominally make copper liquid and aluminum oxide products. We discuss our model of the shock ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model, that includes multi-components for liquid and solid phases of aluminum, copper oxide, copper and aluminum oxide can predict the events observed at the particle scale in the experiments. Supported by HDTRA1-10-1-0020 (DTRA), N000014-12-1-0555 (ONR).

Single crystal growth and characterization of pure and sodium-modified copper tartrate

NASA Astrophysics Data System (ADS)

Quasim, I.; Firdous, A.; Want, B.; Khosa, S. K.; Kotru, P. N.

2008-12-01

Single crystal growth of pure and modified copper tartrate crystals bearing composition (Cu) x(Na) yC 4H 4O 6· nH 2O (where x=1, 0.77, 0.65; y=0, 0.23, 0.35) is achieved using gel technique. The optimum conditions required for the growth of these crystals are worked out. The morphological development of these crystals is studied using optical and scanning electron microscopy. The dominant habit faces of the grown copper tartrate crystals are (0 0 1) and (1 1 1). Calculation of the cell parameters using CRYSFIRE software suggests that the pure copper tartrate crystal belongs to orthorhombic system with space group P2 1/c whereas the modified copper tartrate falls under tetragonal system with the space group P4 2/nbc. The external morphological development is shown to remain unaffected in the modified copper tartrate. The stoichiometric composition of the crystals is established by EDAX analysis, CH analysis, FTIR spectroscopy and thermoanalytical techniques. Thermal analysis of the grown crystals suggests that pure copper tartrate is thermally stable up to 42.84 °C whereas the modified copper tartrate crystals are stable only up to 33.11 and 25.11 °C. Calculation of the percentage weight loss from the thermogram supplemented by EDAX/CH analysis and FTIR spectroscopy suggest that the chemical formula of pure copper tartrate crystal is CuC 4H 4O 6·3H 2O whereas the chemical formula for the modified copper tartrate crystals is (Cu) 0.77(Na) 0.23C 4H 4O 6·3H 2O and (Cu) 0.65(Na) 0.35 C 4H 4O 6·H 2O.

Preparation and characterization of copper oxide nanoparticles decorated carbon nanoparticles using laser ablation in liquid

NASA Astrophysics Data System (ADS)

Khashan, K. S.; Jabir, M. S.; Abdulameer, F. A.

2018-05-01

Carbon nanoparticles CNPs ecorated by copper oxide nano-sized particles would be successfully equipped using technique named pulsed laser ablation in liquid. The XRD pattern proved the presence of phases assigned to carbon and different phases of copper oxide. The chemical structure of the as-prepared nanoparticles samples was decided by Energy Dispersive Spectrum (EDS) measurement. EDS analysis results show the contents of Carbon, Oxygen and Copper in the final product. These nanoparticles were spherical shaped with a size distribution 10 to 80 nm or carbon nanoparticles and 5 to 50 nm for carbon decorated copper oxide nanoparticles, according to Transmission Electron Microscopy (TEM) images and particle-size distribution histogram. It was found that after doping with copper oxide, nanoparticles become smaller and more regular in shape. Optical absorption spectra of prepared nanoparticles were measured using UV–VIS spectroscopy. The absorption spectrum of carbon nanoparticles without doping indicates absorption peak at about 228 nm. After doping with copper oxide, absorption shows appearance of new absorption peak at about (254-264) nm, which is referred to the movement of the charge between 2p and 4s band of Cu2+ ions.

Effects of length dispersity and film fabrication on the sheet resistance of copper nanowire transparent conductors

NASA Astrophysics Data System (ADS)

Borchert, James W.; Stewart, Ian E.; Ye, Shengrong; Rathmell, Aaron R.; Wiley, Benjamin J.; Winey, Karen I.

2015-08-01

Development of thin-film transparent conductors (TC) based on percolating networks of metal nanowires has leaped forward in recent years, owing to the improvement of nanowire synthetic methods and modeling efforts by several research groups. While silver nanowires are the first commercially viable iteration of this technology, systems based on copper nanowires are not far behind. Here we present an analysis of TCs composed of copper nanowire networks on sheets of polyethylene terephthalate that have been treated with various oxide-removing post treatments to improve conductivity. A pseudo-2D rod network modeling approach has been modified to include lognormal distributions in length that more closely reflect experimental data collected from the nanowire TCs. In our analysis, we find that the copper nanowire TCs are capable of achieving comparable electrical performance to silver nanowire TCs with similar dimensions. Lastly, we present a method for more accurately determining the nanowire area coverage in a TC over a large area using Rutherford Backscattering Spectrometry (RBS) to directly measure the metal content in the TCs. These developments will aid research and industry groups alike in the characterization of nanowire based TCs.Development of thin-film transparent conductors (TC) based on percolating networks of metal nanowires has leaped forward in recent years, owing to the improvement of nanowire synthetic methods and modeling efforts by several research groups. While silver nanowires are the first commercially viable iteration of this technology, systems based on copper nanowires are not far behind. Here we present an analysis of TCs composed of copper nanowire networks on sheets of polyethylene terephthalate that have been treated with various oxide-removing post treatments to improve conductivity. A pseudo-2D rod network modeling approach has been modified to include lognormal distributions in length that more closely reflect experimental data collected from the nanowire TCs. In our analysis, we find that the copper nanowire TCs are capable of achieving comparable electrical performance to silver nanowire TCs with similar dimensions. Lastly, we present a method for more accurately determining the nanowire area coverage in a TC over a large area using Rutherford Backscattering Spectrometry (RBS) to directly measure the metal content in the TCs. These developments will aid research and industry groups alike in the characterization of nanowire based TCs. Electronic supplementary information (ESI) available: Contains calibration curve for %T vs. area fraction. See DOI: 10.1039/c5nr03671b

Redox biology response in germinating Phaseolus vulgaris seeds exposed to copper: Evidence for differential redox buffering in seedlings and cotyledon.

PubMed

Karmous, Inès; Trevisan, Rafael; El Ferjani, Ezzeddine; Chaoui, Abdelilah; Sheehan, David

2017-01-01

In agriculture, heavy metal contamination of soil interferes with processes associated with plant growth, development and productivity. Here, we describe oxidative and redox changes, and deleterious injury within cotyledons and seedlings caused by exposure of germinating (Phaseolus vulgaris L. var. soisson nain hâtif) seeds to copper (Cu). Cu induced a marked delay in seedling growth, and was associated with biochemical disturbances in terms of intracellular oxidative status, redox regulation and energy metabolism. In response to these alterations, modulation of activities of antioxidant proteins (thioredoxin and glutathione reductase, peroxiredoxin) occurred, thus preventing oxidative damage. In addition, oxidative modification of proteins was detected in both cotyledons and seedlings by one- and two-dimensional electrophoresis. These modified proteins may play roles in redox buffering. The changes in activities of redox proteins underline their fundamental roles in controlling redox homeostasis. However, observed differential redox responses in cotyledon and seedling tissues showed a major capacity of the seedlings' redox systems to protect the reduced status of protein thiols, thus suggesting quantitatively greater antioxidant protection of proteins in seedlings compared to cotyledon. To our knowledge, this is the first comprehensive redox biology investigation of the effect of Cu on seed germination.

Copper toxicology, oxidative stress and inflammation using zebrafish as experimental model.

PubMed

Pereira, Talita Carneiro Brandão; Campos, Maria Martha; Bogo, Maurício Reis

2016-07-01

Copper is an essential micronutrient and a key catalytic cofactor in a wide range of enzymes. As a trace element, copper levels are tightly regulated and both its deficit and excess are deleterious to the organism. Under inflammatory conditions, serum copper levels are increased and trigger oxidative stress responses that activate inflammatory responses. Interestingly, copper dyshomeostasis, oxidative stress and inflammation are commonly present in several chronic diseases. Copper exposure can be easily modeled in zebrafish; a consolidated model in toxicology with increasing interest in immunity-related research. As a result of developmental, economical and genetic advantages, this freshwater teleost is uniquely suitable for chemical and genetic large-scale screenings, representing a powerful experimental tool for a whole-organism approach, mechanistic studies, disease modeling and beyond. Copper toxicological and more recently pro-inflammatory effects have been investigated in both larval and adult zebrafish with breakthrough findings. Here, we provide an overview of copper metabolism in health and disease and its effects on oxidative stress and inflammation responses in zebrafish models. Copper-induced inflammation is highlighted owing to its potential to easily mimic pro-oxidative and pro-inflammatory features that combined with zebrafish genetic tractability could help further in the understanding of copper metabolism, inflammatory responses and related diseases. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Development of Sediment Quality Values for Puget Sound. Volume 1.

DTIC Science & Technology

1986-09-01

62 cadmium CHROMIUM,63 chromium COPPER ,64 copper IRON ,65 iron LEAD ,66 lead MANGANES ,67 manganese NICKEL ,68 nickel SELENIUM,69 selenium SILVER ,70...BERYLLIU beryllium 67. CADMIUM cadmium 68. CHROMIUM chromium 69. COPPER copper 70. IRON iron 71. LEAD lead 72. MANGANES manganese 73. NICKEL nickel 74...they can also be strongly influenced by iron and manganese oxide and hydrous oxide surfaces (these phases can scavenge metals under oxidizing

Polyethylene oxide film coating enhances lithium cycling efficiency of an anode-free lithium-metal battery.

PubMed

Assegie, Addisu Alemayehu; Cheng, Ju-Hsiang; Kuo, Li-Ming; Su, Wei-Nien; Hwang, Bing-Joe

2018-03-29

The practical implementation of an anode-free lithium-metal battery with promising high capacity is hampered by dendrite formation and low coulombic efficiency. Most notably, these challenges stem from non-uniform lithium plating and unstable SEI layer formation on the bare copper electrode. Herein, we revealed the homogeneous deposition of lithium and effective suppression of dendrite formation using a copper electrode coated with a polyethylene oxide (PEO) film in an electrolyte comprising 1 M LiTFSI, DME/DOL (1/1, v/v) and 2 wt% LiNO3. More importantly, the PEO film coating promoted the formation of a thin and robust SEI layer film by hosting lithium and regulating the inevitable reaction of lithium with the electrolyte. The modified electrode exhibited stable cycling of lithium with an average coulombic efficiency of ∼100% over 200 cycles and low voltage hysteresis (∼30 mV) at a current density of 0.5 mA cm-2. Moreover, we tested the anode-free battery experimentally by integrating it with an LiFePO4 cathode into a full-cell configuration (Cu@PEO/LiFePO4). The new cell demonstrated stable cycling with an average coulombic efficiency of 98.6% and capacity retention of 30% in the 200th cycle at a rate of 0.2C. These impressive enhancements in cycle life and capacity retention result from the synergy of the PEO film coating, high electrode-electrolyte interface compatibility, stable polar oligomer formation from the reduction of 1,3-dioxolane and the generation of SEI-stabilizing nitrite and nitride upon lithium nitrate reduction. Our result opens up a new route to realize anode-free batteries by modifying the copper anode with PEO to achieve ever more demanding yet safe interfacial chemistry and control of dendrite formation.

Glassy carbon electrode modified with polyanilne/ethylenediamine for detection of copper ions

NASA Astrophysics Data System (ADS)

Patil, Harshada K.; Deshmukh, Megha A.; Bodkhe, Gajanan A.; Shirsat, Mahendra D.

2018-05-01

Increasing water pollution is having high concern, since it creates the threats to all leaving organisms of existence. Industrial sewages have not only polluted the main stream lines of water, also the ground level water is having serious contaminations. Heavy metal ions are the pollutants which are not degradable and can be accumulated on living things ultimately the excess accumulation results into the serious concerns. Therefore, it is necessary to develop the sensors which can detect the heavy metal ions up to its maximum contamination limits. Conducting polymers are the materials which possess large application spectra. This investigation reports the electrochemically synthesized polyaniline (PANI) for modification of glassy carbon electrode (GCE). Ethylenediamine (EDA) - chelating ligand used for the modification of polyaniline so as to inculcate the selectivity toward copper ions Cu (II). The electrochemical cyclic voltammetry (CV) was used for the study of redox characteristics of PANI and influence of EDA modification. The result of CV has shown the reduced oxidation and reduction peak currents after modification indicating the domination of EDA. GCE modified with PANI/EDA was then employed for the detection of divalent copper ions and have shown the affinity toward Cu ions. The detection limit achieved was equal to 10mg/lit.

Unsupported single-atom-thick copper oxide monolayers

NASA Astrophysics Data System (ADS)

Yin, Kuibo; Zhang, Yu-Yang; Zhou, Yilong; Sun, Litao; Chisholm, Matthew F.; Pantelides, Sokrates T.; Zhou, Wu

2017-03-01

Oxide monolayers may present unique opportunities because of the great diversity of properties of these materials in bulk form. However, reports on oxide monolayers are still limited. Here we report the formation of single-atom-thick copper oxide layers with a square lattice both in graphene pores and on graphene substrates using aberration-corrected scanning transmission electron microscopy. First-principles calculations find that CuO is energetically stable and its calculated lattice spacing matches well with the measured value. Furthermore, free-standing copper oxide monolayers are predicted to be semiconductors with band gaps ˜3 eV. The new wide-bandgap single-atom-thick copper oxide monolayers usher a new frontier to study the highly diverse family of two-dimensional oxides and explore their properties and their potential for new applications.

The role of oxide structure on copper wire to the rubber adhesion

NASA Astrophysics Data System (ADS)

Su, Yea-Yang; Shemenski, Robert M.

2000-07-01

Most metals have an oxide layer on the surface. However, the structure of the oxide varies with the matrix composition, and depends upon the environmental conditions. A bronze coating, nominal composition of 98.5% Cu and balance of Sn, is applied to steel wire for reinforcing pneumatic tire beads and to provide adhesion to rubber. This work studied the influence of copper oxides on the bronze coating on adhesion during vulcanization. To emphasize the oxide structures, electrolytic tough pitch (ETP) copper wire was used instead of the traditional bronze-coated tire bead wire. Experimental results confirmed the hypothesis that cuprous oxide (Cu 2O) could significantly improve bonding between copper wire and rubber, and demonstrated that the interaction between rubber and oxide layer on wire is an electrochemical reaction.

Effets antibacteriens des nanoparticules de cuivre, oxyde de cuivre et oxyde de fer

NASA Astrophysics Data System (ADS)

Talantikit, Myriam

Population longevity tends to increase in occidental countries inducing an increment in medical implants use. Resistant bacteria may contaminate those implants causing nosocomial infections. Common treatment for bacteria is antibiotic, used mainly for their speed and efficacy. An overuse of antibiotics induced bacteria to be resistant to them. Adding to this issue, when bacteria are in a certain environment, bacteria tend to communicate between themselves and create a biofilm (protective layer). Polysaccharides forming the biofilm don't allow antibiotics to penetrate inside the biofilm. Bacteria in a biofilm are extremely hard to kill. An alternative to resolve all those issues is to use nanoparticles as antimicrobial agents. They are known to have antibacterial effect. But the. The main objective is to study the effects develop "nano-biotics" that can prevent nosocomial infections due to surgical implants. In this project, we evaluated in vitro antibacterial effects of some nanoparticles (copper, copper oxide, superparamagnetic iron oxide, and superparamagnetic iron oxide coupled with nitric oxide (NO) on bacteria. Nanoparticles and microparticles characterizations have been done to determine their size, their composition and their surface chemistry using TEM and FTIR. Different parameters play a crucial role in antibacterial toxicity of particles. First, we adapted microbiological tests to elucidate nanoparticles biotoxicity. Then, pure copper and copper oxide nanoparticles have been studied to determine the importance of nanoparticles composition in toxicity. Size is another important parameter, explaining our interest to study both copper micro and nanoparticles on bacteria (S.aureus and E.coli). Bacterial toxicity of superparamagnetic iron oxide nanoparticles, used as a magnetic vehicle to deliver NO (antibacterial molecule), has been studied. Once NO is delivered, iron oxide nanoparticles still react with bacteria. Finally, copper and copper oxide nanoparticles were in contact with S.aureus biofilm to see their effect and the difference with planktonic bacteria. Our nanoparticles characterizations of copper shows that these nanoparticles are not completely pure but a thin oxide layer at their surface forms, which can lower their toxicity. Our results on the importance of particles size, confirm what was seen in the literature. Nanoparticles seems to be more toxic than microparticles. Superparamagnetic iron oxide nanoparticles results, alone, don't show a big antibacterial effect. Preliminary tests were done on NO coupled nanoparticles, and it seems there is an antibacterial effect. However, NO results are not conclusive because of some technical difficulties during NO attachment on nanoparticles. These studies allowed us to show that copper and copper oxide nanoparticles were a good antibacterial but the dose used might be too important for biomedical applications. Superparamagnetic iron oxide nanoparticles have a low antibacterial effect but are biocompatible. They are an excellent candidate as vehicle for NO delivery to a specific site. These studies are the first effort made to the development of new antimicrobial agents based on metallic nanoparticles. Key words: nanoparticles, copper, oxide copper, biofilm, antibacterial, iron oxide, nitric oxide.

Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films.

PubMed

Chickneyan, Zarui Sara; Briseno, Alejandro L; Shi, Xiangyang; Han, Shubo; Huang, Jiaxing; Zhou, Feimeng

2004-07-01

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.

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

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

Fabrication of Aluminum-Based Thermal Radiation Plate for Thermoelectric Module Using Aluminum Anodic Oxidization and Copper Electroplating.

PubMed

Choi, Yi Taek; Bae, Sung Hwa; Son, Injoon; Sohn, Ho Sang; Kim, Kyung Tae; Ju, Young-Wan

2018-09-01

In this study, electrolytic etching, anodic oxidation, and copper electroplating were applied to aluminum to produce a plate on which a copper circuit for a thermoelectric module was formed. An oxide film insulating layer was formed on the aluminum through anodic oxidation, and platinum was coated by sputtering to produce conductivity. Finally, copper electroplating was performed directly on the substrate. In this structure, the copper plating layer on the insulating layer served as a conductive layer in the circuit. The adhesion of the copper plating layer was improved by electrolytic etching. As a result, the thermoelectric module fabricated in this study showed excellent adhesion and good insulation characteristics. It is expected that our findings can contribute to the manufacture of plates applicable to thermoelectric modules with high dissipation performance.

Thermal and Surface Evaluation on The Process of Forming a Cu2O/CuO Semiconductor Photocatalyst on a Thin Copper Plate

NASA Astrophysics Data System (ADS)

Zainul, R.; Oktavia, B.; Dewata, I.; Efendi, J.

2018-04-01

This research aims to investigate the process of forming a multi-scale copper oxide semiconductor (CuO/Cu2O) through a process of calcining a copper plate. The changes that occur during the formation of the oxide are thermally and surface evaluated. Evaluation using Differential Thermal Analysis (DTA) obtained by surface change of copper plate happened at temperature 380°C. Calcination of oxide formation was carried out at temperature 380°C for 1 hour. Surface evaluation process by using Scanning Electron Microscope (SEM) surface and cross-section, to determine diffusion of oxide formation on copper plate. The material composition is monitored by XRF and XRD to explain the process of structural and physical changes of the copper oxide plate formed during the heating process. The thickness of Cu plates used is 200-250 μm. SEM analysis results, the oxygen atom interruption region is in the range of 20-30 μm, and diffuses deeper during thermal oxidation process. The maximum diffusion depth of oxygen atoms reaches 129 μm.

The flavinyl transferase ApbE of Pseudomonas stutzeri matures the NosR protein required for nitrous oxide reduction.

PubMed

Zhang, Lin; Trncik, Christian; Andrade, Susana L A; Einsle, Oliver

2017-02-01

The copper-containing enzyme nitrous oxide reductase (N 2 OR) catalyzes the transformation of nitrous oxide (N 2 O) to dinitrogen (N 2 ) in microbial denitrification. Several accessory factors are essential for assembling the two copper sites Cu A and Cu Z , and for maintaining the activity. In particular, the deletion of either the transmembrane iron-sulfur flavoprotein NosR or the periplasmic protein NosX, a member of the ApbE family, abolishes N 2 O respiration. Here we demonstrate through biochemical and structural studies that the ApbE protein from Pseudomonas stutzeri, where the nosX gene is absent, is a monomeric FAD-binding protein that can serve as the flavin donor for NosR maturation via covalent flavinylation of a threonine residue. The flavin transfer reaction proceeds both in vivo and in vitro to generate post-translationally modified NosR with covalently bound FMN. Only FAD can act as substrate and the reaction requires a divalent cation, preferably Mg 2+ that was also present in the crystal structure. In addition, the reaction is species-specific to a certain extent. Copyright © 2016 Elsevier B.V. All rights reserved.

Aggregation and fusion of modified low density lipoprotein.

PubMed

Pentikäinen, M O; Lehtonen, E M; Kovanen, P T

1996-12-01

In atherogenesis, low density lipoprotein (LDL, diameter 22 nm) accumulates in the extracellular space of the arterial intima in the form of aggregates of lipid droplets (droplet diameter up to 400 nm). Here we studied the effects of various established in vitro LDL modifications on LDL aggregation and fusion. LDL was subjected to vortexing, oxidation by copper ions, proteolysis by alpha-chymotrypsin, lipolysis by sphingomyelinase, and nonenzymatic glycosylation, and was induced to form adducts with malondialdehyde or complexes with anti-apoB-100 antibodies. To assess the amount of enlarged LDL-derived structures formed (due to aggregation or fusion), we measured the turbidity of solutions containing modified LDL, and quantified the proportion of modified LDL that 1) sedimented at low-speed centrifugation (14,000 g), 2) floated at an increased rate at high-speed centrifugation (rate zonal flotation at 285,000 gmax), 3) were excluded in size-exclusion column chromatography (exclusion limit 40 MDa), or 4) failed to enter into 0.5%. Fast Lane agarose gel during electrophoresis. To detect whether particle fusion had contributed to the formation of the enlarged LDL-derived structures, particle morphology was examined using negative staining and thin-section transmission electron microscopy. We found that 1) aggregation was induced by the formation of LDL-antibody complexes, malondialdehyde treatment, and glycosylation of LDL; 2) fusion of LDL was induced by proteolysis of LDL by alpha-chymotrypsin; and 3) aggregation and fusion of LDL were induced by vortexing, oxidation by copper ions, and lipolysis by sphingomyclinase of LDL. The various modifications of LDL differed in their ability to induce aggregation and fusion.

Comparison between the electrocatalytic properties of different metal ion phthalocyanines and porphyrins towards the oxidation of hydroxide.

PubMed

De Wael, Karolien; Adriaens, Annemie

2008-02-15

This work reports on the electrocatalytic oxidation of hydroxide using different central metal ion phthalocyanines and porphyrins immobilized on gold electrodes. The apparent electrocatalytic activity of cobalt phthalocyanine or porphyrin modified electrodes was found to be the greatest among the present series of metal ion macrocycles investigated. Copper and unmetallated phthalocyanine or porphyrin modified electrodes show no electrocatalytic behaviour towards hydroxide, such as bare gold. A possible mechanism for the enhanced reactivity of cobalt ion macrocycles towards the oxygen evolution is given. It is also stated that the electrocatalytic activity towards an adsorbate involves several aspects, such as the coordination state of the central metal ion, the nature of the ligand, the stability of the complexes, the number of d electrons, the energy of orbitals and the strength of the bonding between the central metal ion and the axial ligand.

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

DOE PAGES

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

2016-12-16

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

Corrosion Behavior of Plasma-Passivated Cu

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

Barbour, J.C.; Braithwaite, J.W.; Son, K.A.

1999-07-09

A new approach is being pursued to study corrosion in Cu alloy systems by using combinatorial analysis combined with microscopic experimentation (the Combinatorial Microlab) to determine mechanisms for copper corrosion in air. Corrosion studies are inherently difficult because of complex interactions between materials and environment, forming a multidimensional phase space of corrosion variables. The Combinatorial Microlab was specifically developed to address the mechanism of Cu sulfidation, which is an important reliability issue for electronic components. This approach differs from convention by focusing on microscopic length scales, the relevant scale for corrosion. During accelerated aging, copper is exposed to a varietymore » of corrosive environments containing sulfidizing species that cause corrosion. A matrix experiment was done to determine independent and synergistic effects of initial Cu oxide thickness and point defect density. The CuO{sub x} was controlled by oxidizing Cu in an electron cyclotron resonance (ECR) O{sub 2} plasma, and the point defect density was modified by Cu ion irradiation. The matrix was exposed to 600 ppb H{sub 2}S in 65% relative humidity air atmosphere. This combination revealed the importance of oxide quality in passivating Cu and prevention of the sulfidizing reaction. A native oxide and a defect-laden ECR oxide both react at 20 C to form a thick Cu{sub 2}S layer after exposure to H{sub 2}S, while different thicknesses of as-grown ECR oxide stop the formation of Cu{sub 2}S. The species present in the ECR oxide will be compared to that of an air oxide, and the sulfide layer growth rate will be presented.« less

The effect of copper deficiency on fetal growth and liver anti-oxidant capacity in the Cohen diabetic rat model

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

Ergaz, Zivanit, E-mail: zivanit@hadassah.org.il; Shoshani-Dror, Dana; Guillemin, Claire

High sucrose low copper diet induces fetal growth restriction in the three strains of the Cohen diabetic rats: an inbred copper deficient resistant (CDr), an inbred copper deficient sensitive (CDs that become diabetic on high sucrose low copper diet -HSD) and an outbred Wistar derived Sabra rats. Although those growth restricted fetuses also exhibit increased oxidative stress, antioxidants do not restore normal growth. In the present study, we evaluated the role of copper deficiency in the HSD induced fetal growth restriction by adding to the drinking water of the rats 1 ppm or 2 ppm of copper throughout their pregnancy.more » Fetal and placental growth in correlation with fetal liver copper content and anti-oxidant capacity was evaluated on day 21 of pregnancy. HSD compared to regular chow induced fetal growth restriction, which was most significant in the Cohen diabetic sensitive animals. The addition of 1 ppm and 2 ppm copper to the drinking water normalized fetal growth in a dose dependent manner and reduced the degree of hyperglycemia in the diabetes sensitive rats. The CDs fetuses responded to the HSD with lower catalase like activity, and less reduced superoxide dismutase levels compared to the Sabra strain, and had high malondialdehyde levels even when fed regular chow. Immunostaining was higher for nitrotyrosine among the CDr and higher for hypoxia factor 1 α among the CDs. We conclude that in our model of dietary-induced fetal growth restriction, copper deficiency plays a major etiologic role in the decrease of fetal growth and anti-oxidant capacity. -- Highlights: ► High sucrose low copper diet restricted fetal growth in the Cohen diabetic rat model ► Maternal copper blood levels directly correlated with fetal liver copper content ► Copper supplementation decreased embryonic resorption in the inbred strains ► Copper supplementation reduced hyperglycemia in the sucrose sensitive inbred strain ► Copper supplementation alleviated growth restriction and oxidative stress of liver.« less

Copper@carbon coaxial nanowires synthesized by hydrothermal carbonization process from electroplating wastewater and their use as an enzyme-free glucose sensor.

PubMed

Zhao, Yuxin; He, Zhaoyang; Yan, Zifeng

2013-01-21

In the pursuit of electrocatalysts with great economic and ecological values for non-enzymatic glucose sensors, one-dimensional copper@carbon (Cu@C) core-shell coaxial nanowires (NWs) have been successfully prepared via a simple continuous flow wet-chemistry approach from electroplating wastewater. The as-obtained products were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectroscopy and Raman spectroscopy. The electrocatalytic activity of the modified electrodes by Cu@C NWs towards glucose oxidation was investigated by cyclic voltammetry and chronoamperometry. It was found that the as-obtained Cu@C NWs showed good electrochemical properties and could be used as an electrochemical sensor for the detection of glucose molecules. Compared to the other electrodes including the bare Nafion/glassy carbon electrode (GCE) and several hot hybrid nanostructures modified GCE, a substantial decrease in the overvoltage of the glucose oxidation was observed at the Cu@C NWs electrodes with oxidation starting at ca. 0.20 V vs. Ag/AgCl (3 M KCl). At an applied potential of 0.65 V, Cu@C NWs electrodes had a high and reproducible sensitivity of 437.8 µA cm(-2) mM(-1) to glucose. Linear responses were obtained with a detection limit of 50 nM. More importantly, the proposed electrode also had good stability, high resistance against poisoning by chloride ion and commonly interfering species. These good analytical performances make Cu@C NWs promising for the future development of enzyme-free glucose sensors.

Wilson Disease: Epigenetic effects of choline supplementation on phenotype and clinical course in a mouse model.

PubMed

Medici, Valentina; Kieffer, Dorothy A; Shibata, Noreene M; Chima, Harpreet; Kim, Kyoungmi; Canovas, Angela; Medrano, Juan F; Islas-Trejo, Alma D; Kharbanda, Kusum K; Olson, Kristin; Su, Ruijun J; Islam, Mohammad S; Syed, Raisa; Keen, Carl L; Miller, Amy Y; Rutledge, John C; Halsted, Charles H; LaSalle, Janine M

2016-11-01

Wilson disease (WD), a genetic disorder affecting copper transport, is characterized by hepatic and neurological manifestations with variable and often unpredictable presentation. Global DNA methylation in liver was previously modified by dietary choline in tx-j mice, a spontaneous mutant model of WD. We therefore hypothesized that the WD phenotype and hepatic gene expression of tx-j offspring could be modified by maternal methyl supplementation during pregnancy. In an initial experiment, female tx-j mice or wild type mice were fed control or choline-supplemented diets 2 weeks prior to mating through embryonic day 17. Transcriptomic analysis (RNA-seq) on embryonic livers revealed tx-j-specific differences in genes related to oxidative phosphorylation, mitochondrial dysfunction, and the neurological disorders Huntington's disease and Alzheimer disease. Maternal choline supplementation restored the transcript levels of a subset of genes to wild type levels. In a separate experiment, a group of tx-j offspring continued to receive choline-supplemented or control diets, with or without the copper chelator penicillamine (PCA) for 12 weeks until 24 weeks of age. Combined choline supplementation and PCA treatment of 24-week-old tx-j mice was associated with increased liver transcript levels of methionine metabolism and oxidative phosphorylation-related genes. Sex differences in gene expression within each treatment group were also observed. These results demonstrate that the transcriptional changes in oxidative phosphorylation and methionine metabolism genes in WD that originate during fetal life are, in part, prevented by prenatal maternal choline supplementation, a finding with potential relevance to preventive treatments of WD.

Wilson Disease: Epigenetic effects of choline supplementation on phenotype and clinical course in a mouse model

PubMed Central

Medici, Valentina; Kieffer, Dorothy A.; Shibata, Noreene M.; Chima, Harpreet; Kim, Kyoungmi; Canovas, Angela; Medrano, Juan F.; Islas-Trejo, Alma D.; Kharbanda, Kusum K.; Olson, Kristin; Su, Ruijun J.; Islam, Mohammad S.; Syed, Raisa; Keen, Carl L.; Miller, Amy Y.; Rutledge, John C.; Halsted, Charles H.; LaSalle, Janine M.

2016-01-01

ABSTRACT Wilson disease (WD), a genetic disorder affecting copper transport, is characterized by hepatic and neurological manifestations with variable and often unpredictable presentation. Global DNA methylation in liver was previously modified by dietary choline in tx-j mice, a spontaneous mutant model of WD. We therefore hypothesized that the WD phenotype and hepatic gene expression of tx-j offspring could be modified by maternal methyl supplementation during pregnancy. In an initial experiment, female tx-j mice or wild type mice were fed control or choline-supplemented diets 2 weeks prior to mating through embryonic day 17. Transcriptomic analysis (RNA-seq) on embryonic livers revealed tx-j-specific differences in genes related to oxidative phosphorylation, mitochondrial dysfunction, and the neurological disorders Huntington's disease and Alzheimer disease. Maternal choline supplementation restored the transcript levels of a subset of genes to wild type levels. In a separate experiment, a group of tx-j offspring continued to receive choline-supplemented or control diets, with or without the copper chelator penicillamine (PCA) for 12 weeks until 24 weeks of age. Combined choline supplementation and PCA treatment of 24-week-old tx-j mice was associated with increased liver transcript levels of methionine metabolism and oxidative phosphorylation-related genes. Sex differences in gene expression within each treatment group were also observed. These results demonstrate that the transcriptional changes in oxidative phosphorylation and methionine metabolism genes in WD that originate during fetal life are, in part, prevented by prenatal maternal choline supplementation, a finding with potential relevance to preventive treatments of WD. PMID:27611852

A novel anti-influenza copper oxide containing respiratory face mask.

PubMed

Borkow, Gadi; Zhou, Steve S; Page, Tom; Gabbay, Jeffrey

2010-06-25

Protective respiratory face masks protect the nose and mouth of the wearer from vapor drops carrying viruses or other infectious pathogens. However, incorrect use and disposal may actually increase the risk of pathogen transmission, rather than reduce it, especially when masks are used by non-professionals such as the lay public. Copper oxide displays potent antiviral properties. A platform technology has been developed that permanently introduces copper oxide into polymeric materials, conferring them with potent biocidal properties. We demonstrate that impregnation of copper oxide into respiratory protective face masks endows them with potent biocidal properties in addition to their inherent filtration properties. Both control and copper oxide impregnated masks filtered above 99.85% of aerosolized viruses when challenged with 5.66+/-0.51 and 6.17+/-0.37 log(10)TCID(50) of human influenza A virus (H1N1) and avian influenza virus (H9N2), respectively, under simulated breathing conditions (28.3 L/min). Importantly, no infectious human influenza A viral titers were recovered from the copper oxide containing masks within 30 minutes (< or = 0.88 log(10)TCID(50)), while 4.67+/-1.35 log(10)TCID(50) were recovered from the control masks. Similarly, the infectious avian influenza titers recovered from the copper oxide containing masks were < or = 0.97+/-0.01 log(10)TCID(50) and from the control masks 5.03+/-0.54 log(10)TCID(50). The copper oxide containing masks successfully passed Bacterial Filtration Efficacy, Differential Pressure, Latex Particle Challenge, and Resistance to Penetration by Synthetic Blood tests designed to test the filtration properties of face masks in accordance with the European EN 14683:2005 and NIOSH N95 standards. Impregnation of copper oxide into respiratory protective face masks endows them with potent anti-influenza biocidal properties without altering their physical barrier properties. The use of biocidal masks may significantly reduce the risk of hand or environmental contamination, and thereby subsequent infection, due to improper handling and disposal of the masks.

Oxidation Potentials in Matte Smelting of Copper and Nickel

NASA Astrophysics Data System (ADS)

Matousek, Jan W.

2014-09-01

The oxidation potential, given as the base-ten logarithm of the oxygen partial pressure in bars and the temperature [log pO2/ T, °C], defines the state of oxidation of pyrometallurgical extraction and refining processes. This property varies from copper making, [-6/1150]; to lead/zinc smelting, [-10/1200]; to iron smelting, [-13/1600]. The current article extends the analysis to the smelting of copper and nickel/copper sulfide concentrates to produce mattes of the type Cu(Ni)FeS(O) and iron silicate slags, FeOxSiO2—with oxidation potentials of [-7.5/1250].

Comparison of the Oxidation Rates of Some New Copper Alloys

NASA Technical Reports Server (NTRS)

Ogbuji, Linus U. J. Thomas; Humphrey, Donald L.

2002-01-01

Copper alloys were studied for oxidation resistance and mechanisms between 550 and 700 C, in reduced-oxygen environments expected in rocket engines, and their oxidation behaviors compared to that of pure copper. They included two dispersion-strengthened alloys (precipitation-strengthened and oxide-dispersion strengthened, respectively) and one solution-strengthened alloy. In all cases the main reaction was oxidation of Cu into Cu2O and CuO. The dispersion-strengthened alloys were superior to both Cu and the solution-strengthened alloy in oxidation resistance. However, factors retarding oxidation rates seemed to be different for the two dispersion-strengthened alloys.

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

Eilert, André; Roberts, F. Sloan; Friebel, Daniel

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Highly Conductive and Reliable Copper-Filled Isotropically Conductive Adhesives Using Organic Acids for Oxidation Prevention

NASA Astrophysics Data System (ADS)

Chen, Wenjun; Deng, Dunying; Cheng, Yuanrong; Xiao, Fei

2015-07-01

The easy oxidation of copper is one critical obstacle to high-performance copper-filled isotropically conductive adhesives (ICAs). In this paper, a facile method to prepare highly reliable, highly conductive, and low-cost ICAs is reported. The copper fillers were treated by organic acids for oxidation prevention. Compared with ICA filled with untreated copper flakes, the ICA filled with copper flakes treated by different organic acids exhibited much lower bulk resistivity. The lowest bulk resistivity achieved was 4.5 × 10-5 Ω cm, which is comparable to that of commercially available Ag-filled ICA. After 500 h of 85°C/85% relative humidity (RH) aging, the treated ICAs showed quite stable bulk resistivity and relatively stable contact resistance. Through analyzing the results of x-ray diffraction, x-ray photoelectron spectroscopy, and thermogravimetric analysis, we found that, with the assistance of organic acids, the treated copper flakes exhibited resistance to oxidation, thus guaranteeing good performance.

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

PubMed

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

2014-08-30

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

Tuning of structural, light emission and wetting properties of nanostructured copper oxide-porous silicon matrix formed on electrochemically etched copper-coated silicon substrates

NASA Astrophysics Data System (ADS)

Naddaf, M.

2017-01-01

Matrices of copper oxide-porous silicon nanostructures have been formed by electrochemical etching of copper-coated silicon surfaces in HF-based solution at different etching times (5-15 min). Micro-Raman, X-ray diffraction and X-ray photoelectron spectroscopy results show that the nature of copper oxide in the matrix changes from single-phase copper (I) oxide (Cu2O) to single-phase copper (II) oxide (CuO) on increasing the etching time. This is accompanied with important variation in the content of carbon, carbon hydrides, carbonyl compounds and silicon oxide in the matrix. The matrix formed at the low etching time (5 min) exhibits a single broad "blue" room-temperature photoluminescence (PL) band. On increasing the etching time, the intensity of this band decreases and a much stronger "red" PL band emerges in the PL spectra. The relative intensity of this band with respect to the "blue" band significantly increases on increasing the etching time. The "blue" and "red" PL bands are attributed to Cu2O and porous silicon of the matrix, respectively. In addition, the water contact angle measurements reveal that the hydrophobicity of the matrix surface can be tuned from hydrophobic to superhydrophobic state by controlling the etching time.

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

NASA Astrophysics Data System (ADS)

Zhang, Dongfang; Zeng, Fanbin

2011-06-01

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

Fabrication and characterization of copper oxide (CuO)–gold (Au)–titania (TiO{sub 2}) and copper oxide (CuO)–gold (Au)–indium tin oxide (ITO) nanowire heterostructures

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

Chopra, Nitin, E-mail: nchopra@eng.ua.edu; Department of Biological Sciences, The University of Alabama, Tuscaloosa, AL 35487; Shi, Wenwu

2014-10-15

Nanoscale heterostructures composed of standing copper oxide nanowires decorated with Au nanoparticles and shells of titania and indium tin oxide were fabricated. The fabrication process involved surfactant-free and wet-chemical nucleation of gold nanoparticles on copper oxide nanowires followed by a line-of-sight sputtering of titania or indium tin oxide. The heterostructures were characterized using high resolution electron microscopy, diffraction, and energy dispersive spectroscopy. The interfaces, morphologies, crystallinity, phases, and chemical compositions were analyzed. The process of direct nucleation of gold nanoparticles on copper oxide nanoparticles resulted in low energy interface with aligned lattice for both the components. Coatings of polycrystalline titaniamore » or amorphous indium tin oxide were deposited on standing copper oxide nanowire–gold nanoparticle heterostructures. Self-shadowing effect due to standing nanowire heterostructures was observed for line-of-sight sputter deposition of titania or indium tin oxide coatings. Finally, the heterostructures were studied using Raman spectroscopy and ultraviolet–visible spectroscopy, including band gap energy analysis. Tailing in the band gap energy at longer wavelengths (or lower energies) was observed for the nanowire heterostructures. - Highlights: • Heterostructures comprised of CuO nanowires coated with Au nanoparticles. • Au nanoparticles exhibited nearly flat and low energy interface with nanowire. • Heterostructures were further sputter-coated with oxide shell of TiO{sub 2} or ITO. • The process resulted in coating of polycrystalline TiO{sub 2} and amorphous ITO shell.« less

Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy

DOE PAGES

Eilert, André; Roberts, F. Sloan; Friebel, Daniel; ...

2016-04-04

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Low-Temperature Oxidation-Free Selective Laser Sintering of Cu Nanoparticle Paste on a Polymer Substrate for the Flexible Touch Panel Applications.

PubMed

Kwon, Jinhyeong; Cho, Hyunmin; Eom, Hyeonjin; Lee, Habeom; Suh, Young Duk; Moon, Hyunjin; Shin, Jaeho; Hong, Sukjoon; Ko, Seung Hwan

2016-05-11

Copper nanomaterials suffer from severe oxidation problem despite the huge cost effectiveness. The effect of two different processes for conventional tube furnace heating and selective laser sintering on copper nanoparticle paste is compared in the aspects of chemical, electrical and surface morphology. The thermal behavior of the copper thin films by furnace and laser is compared by SEM, XRD, FT-IR, and XPS analysis. The selective laser sintering process ensures low annealing temperature, fast processing speed with remarkable oxidation suppression even in air environment while conventional tube furnace heating experiences moderate oxidation even in Ar environment. Moreover, the laser-sintered copper nanoparticle thin film shows good electrical property and reduced oxidation than conventional thermal heating process. Consequently, the proposed selective laser sintering process can be compatible with plastic substrate for copper based flexible electronics applications.

Solution-processed copper-nickel nanowire anodes for organic solar cells

NASA Astrophysics Data System (ADS)

Stewart, Ian E.; Rathmell, Aaron R.; Yan, Liang; Ye, Shengrong; Flowers, Patrick F.; You, Wei; Wiley, Benjamin J.

2014-05-01

This work describes a process to make anodes for organic solar cells from copper-nickel nanowires with solution-phase processing. Copper nanowire films were coated from solution onto glass and made conductive by dipping them in acetic acid. Acetic acid removes the passivating oxide from the surface of copper nanowires, thereby reducing the contact resistance between nanowires to nearly the same extent as hydrogen annealing. Films of copper nanowires were made as oxidation resistant as silver nanowires under dry and humid conditions by dipping them in an electroless nickel plating solution. Organic solar cells utilizing these completely solution-processed copper-nickel nanowire films exhibited efficiencies of 4.9%.This work describes a process to make anodes for organic solar cells from copper-nickel nanowires with solution-phase processing. Copper nanowire films were coated from solution onto glass and made conductive by dipping them in acetic acid. Acetic acid removes the passivating oxide from the surface of copper nanowires, thereby reducing the contact resistance between nanowires to nearly the same extent as hydrogen annealing. Films of copper nanowires were made as oxidation resistant as silver nanowires under dry and humid conditions by dipping them in an electroless nickel plating solution. Organic solar cells utilizing these completely solution-processed copper-nickel nanowire films exhibited efficiencies of 4.9%. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01024h

High temperature mechanical properties of a zirconium-modified, precipitation- strengthened nickel, 30 percent copper alloy

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1974-01-01

A precipitation-strengthened Monel-type alloy has been developed through minor alloying additions of zirconium to a base Ni-30Cu alloy. The results of this exploratory study indicate that thermomechanical processing of a solution-treated Ni-30Cu-0.2Zr alloy produced a dispersion of precipitates. The precipitates have been tentatively identified as a Ni5Zr compound. A comparison of the mechanical properties, as determined by testing in air, of the zirconium-modified alloy to those of a Ni-30Cu alloy reveals that the precipitation-strengthened alloy has improved tensile properties to 1200 K and improved stress-rupture properties to 1100 K. The oxidation characteristics of the modified alloy appeared to be equivalent to those of the base Ni-30Cu alloy.

Initial stage corrosion of nanocrystalline copper particles and thin films

NASA Astrophysics Data System (ADS)

Tao, Weimin

1997-12-01

Corrosion behavior is an important issue in nanocrystalline materials research and development. A very fine grain size is expected to have significant effects on the corrosion resistance of these novel materials. However, both the macroscopic corrosion properties and the corresponding structure evolution during corrosion have not been fully studied. Under such circumstances, conducting fundamental research in this area is important and necessary. In this study, high purity nanocrystalline and coarse-grained copper were selected as our sample material, sodium nitrite aqueous solution at room temperature and air at a high temperature were employed as corrosive environments. The weight loss testing and electrochemical methods were used to obtain the macroscopic corrosion properties, whereas the high resolution transmission electron microscope was employed for the structure analysis. The weight loss tests indicate that the corrosion rate of nanocrystalline copper is about 5 times higher than that of coarse-grained copper at the initial stage of corrosion. The electrochemical measurements show that the corrosion potential of the nanocrystalline copper has a 230 mV negative shift in comparison with that of the coarse-grained copper. The nanocrystalline copper also exhibits a significantly higher exchange current density than the coarse-grained copper. High resolution TEM revealed that the surface structure changes at the initial stage of corrosion. It was found that the first copper oxide layer formed on the surface of nanocrystalline copper thin film contains a large density of high angle grain boundaries, whereas that formed on the surface of coarse-grained copper shows highly oriented oxide nuclei and appears to show a strong tendency for forming low angle grain boundaries. A correlation between the macroscopic corrosion properties and the structure characteristics is proposed for the nanocrystalline copper based on the concept of the "apparent" exchange current density associated with mass transport of ions in the oxide layer. A hypothesis is developed that the high corrosion rate of the nanocrystalline copper is closely associated with the structure of the copper oxide layer. Therefore, a high "apparent" exchange current density for the nanocrystalline copper is associated with the high angle grain boundary structure in the initial oxide layer. Additional structure analysis was also carried out: (a) High resolution TEM imaging has provided a cross sectional view of the epitaxial interface between nanocrystalline copper and copper (I) oxide and explicitly discloses the presence of interface defects such as misfit dislocations. Based on this observation, a mechanism was proposed to explain the Cu/Cusb2O interface misfit accommodation. This appears to be the first time this interface has been directly examined. (b) A nanocrystalline analogue to a cross-section of Gwathmey's copper single crystal sphere was revealed by high resolution TEM imaging. A partially oxidized nanocrystalline copper particle is used to examine the variation of the Cu/Cusb2O orientation relationship with respect to changes in surface orientation. A new orientation relationship, Cu (011) //Cusb2O (11), ˜ Cu(011)//Cusb2O(111), was found for the oxidation of nanocrystalline copper.

Catalytic production of metal carbonyls from metal oxides

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

1984-01-01

This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

Catalytic production of metal carbonyls from metal oxides

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Foran, M.T.

1984-01-06

This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150 to 260/sup 0/C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO/sub 4/ and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect. 3 tables.

Probing the importance of the hemilabile site of bis(phosphine) monoxide ligands in the copper-catalyzed addition of diethylzinc to N-phosphinoylimines: discovery of new effective chiral ligands.

PubMed

Bonnaventure, Isabelle; Charette, André B

2008-08-15

The hemilabile ligand Me-DuPHOS(O) 2 has proven to be a successful ligand for the copper-catalyzed addition of diethylzinc to N-phosphinoylimines. The corresponding alpha-chiral amines were obtained in high yields (80-98%) and enantiomeric ratios (19.0:1 to 99.0:1 er). Furthermore, this Cu* 2 catalytic system has been shown to be effective in the addition of diethylzinc to nitroalkenes and in the reduction of beta,beta-disubstituted vinyl phenyl sulfones. This paper describes a general structure/selectivity study in which the three ligand subunits (chiral phospholane-linker-labile coordinating group (Z)) are systematically modified and tested in the copper-catalyzed addition of diethylzinc to the N-phosphinoylimine 1 derived from benzaldehyde. This study led to the discovery of a new class of effective chiral ligands that combine a chiral phospholane unit and an achiral phosphine oxide.

Developing of a magnetite film of carboxymethyl cellulose grafted carboxymethyl polyvinyl alcohol (CMC-g-CMPVA) for copper removal.

PubMed

Dahlan, Nuraina Anisa; Veeramachineni, Anand Kumar; Langford, Steven James; Pushpamalar, Janarthanan

2017-10-01

Crosslinked carboxymethyl cellulose grafted carboxymethyl polyvinyl alcohol (CMC-g-CMPVA) was loaded with modified magnetite iron oxide (Fe 3 O 4 ) nanoparticles to synthesise a new and easily separable adsorbent for the removal of copper (II) ions from water. The novel adsorbents were characterised by the presence of the functional group, surface morphology, crystallinity and magnetic property. The equilibrium time from the adsorption studies was found to be less than 240min for both film and bead forms while the rate of Cu 2+ removal decreased as the initial Cu 2+ concentration increased. In addition, CMC-g-CMPVA film loaded with Fe 3 O 4 /SiO 2 nanoparticles was the best adsorbent with maximum adsorption capacity of 35.34mg/g and exhibited a reusable potential. The properties exhibited by the new heterogeneous material is a promising adsorbent for the removal and recovery of copper (II) from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mechanical tearing of graphene on an oxidizing metal surface.

PubMed

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

2015-12-11

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

Low-cost optical fabrication of flexible copper electrode via laser-induced reductive sintering and adhesive transfer

NASA Astrophysics Data System (ADS)

Back, Seunghyun; Kang, Bongchul

2018-02-01

Fabricating copper electrodes on heat-sensitive polymer films in air is highly challenging owing to the need of expensive copper nanoparticles, rapid oxidation of precursor during sintering, and limitation of sintering temperature to prevent the thermal damage of the polymer film. A laser-induced hybrid process of reductive sintering and adhesive transfer is demonstrated to cost-effectively fabricate copper electrode on a polyethylene film with a thermal resistance below 100 °C. A laser-induced reductive sintering process directly fabricates a high-conductive copper electrode onto a glass donor from copper oxide nanoparticle solution via photo-thermochemical reduction and agglomeration of copper oxide nanoparticles. The sintered copper patterns were transferred in parallel to a heat-sensitive polyethylene film through self-selective surface adhesion of the film, which was generated by the selective laser absorption of the copper pattern. The method reported here could become one of the most important manufacturing technologies for fabricating low-cost wearable and disposable electronics.

Thin film photovoltaic cells having increased durability and operating life and method for making same

DOEpatents

Barnett, Allen M.; Masi, James V.; Hall, Robert B.

1980-12-16

A solar cell having a copper-bearing absorber is provided with a composite transparent encapsulating layer specifically designed to prevent oxidation of the copper sulfide. In a preferred embodiment, the absorber is a layer of copper sulfide and the composite layer comprises a thin layer of copper oxide formed on the copper sulfide and a layer of encapsulating glass formed on the oxide. It is anticipated that such devices, when exposed to normal operating conditions of various terrestrial applications, can be maintained at energy conversion efficiencies greater than one-half the original conversion efficiency for periods as long as thirty years.

Transformations of C2-C4 alcohols on the surface of a copper catalyst

NASA Astrophysics Data System (ADS)

Magaeva, A. A.; Lyamina, G. V.; Sudakova, N. N.; Shilyaeva, L. P.; Vodyankina, O. V.

2007-10-01

The interaction of monoatomic alcohols C2-C4 with the surface of a copper catalyst preliminarily oxidized under various conditions was studied by the temperature-programmed reaction method to determine the detailed mechanism of partial oxidation. The conditions of oxygen preadsorption on the surface of copper for the preparation of the desired products were determined. The selective formation of carbonyl compounds was shown to occur at the boundary between reduced and oxidized copper surface regions. The role played by Cu2O was the deep oxidation of alcohols to CO2. Alcohols with branched hydrocarbon structures experienced parallel partial oxidation and dehydrogenation, which was related to the high stability of intermediate keto-type compounds.

Auger electron spectroscopy and Rutherford backscattering studies of copper in 2024-T3 aluminum following electrochemical anodization in phosphoric acid

NASA Astrophysics Data System (ADS)

Solomon, J. S.

1981-05-01

The effects of the electrochemical anodization of dioxidized 2024-T3 aluminum on copper were characterized by Auger electron spectroscopy and Rutherford backscattering. Anodization was performed in phosphoric acid at constant potential. Data is presented which shows that constant potential anodization of 2024-T3 is more efficient than aluminum in terms of oxide growth rates for short anodization times. However the maximum anodic oxide thickness achievable on the alloy is less than the pure metal. Copper is shown to be enriched at the oxide metal interface because of its diffusion from the bulk during anodization. The presence of copper at the oxide-metal interface is shown to affect oxide morphology.

Metal-enhanced fluorescence platforms based on plasmonic ordered copper arrays: wavelength dependence of quenching and enhancement effects.

PubMed

Sugawa, Kosuke; Tamura, Takahiro; Tahara, Hironobu; Yamaguchi, Daisuke; Akiyama, Tsuyoshi; Otsuki, Joe; Kusaka, Yasuyuki; Fukuda, Nobuko; Ushijima, Hirobumi

2013-11-26

Ordered arrays of copper nanostructures were fabricated and modified with porphyrin molecules in order to evaluate fluorescence enhancement due to the localized surface plasmon resonance. The nanostructures were prepared by thermally depositing copper on the upper hemispheres of two-dimensional silica colloidal crystals. The wavelength at which the surface plasmon resonance of the nanostructures was generated was tuned to a longer wavelength than the interband transition region of copper (>590 nm) by controlling the diameter of the underlying silica particles. Immobilization of porphyrin monolayers onto the nanostructures was achieved via self-assembly of 16-mercaptohexadecanoic acid, which also suppressed the oxidation of the copper surface. The maximum fluorescence enhancement of porphyrin by a factor of 89.2 was achieved as compared with that on a planar Cu plate (CuP) due to the generation of the surface plasmon resonance. Furthermore, it was found that while the fluorescence from the porphyrin was quenched within the interband transition region, it was efficiently enhanced at longer wavelengths. It was demonstrated that the enhancement induced by the proximity of the fluorophore to the nanostructures was enough to overcome the highly efficient quenching effects of the metal. From these results, it is speculated that the surface plasmon resonance of copper has tremendous potential for practical use as high functional plasmonic sensor and devices.

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2011 CFR

2011-04-01

.... Manganese phosphate (dibasic). Manganese sulfate. Manganous oxide. Zinc Zinc acetate. Zinc carbonate. Zinc chloride. Zinc oxide. Zinc sulfate. ... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2010 CFR

2010-04-01

.... Manganese phosphate (dibasic). Manganese sulfate. Manganous oxide. Zinc Zinc acetate. Zinc carbonate. Zinc chloride. Zinc oxide. Zinc sulfate. ... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper...

Easy route to superhydrophobic copper-based wire-guided droplet microfluidic systems.

PubMed

Mumm, Florian; van Helvoort, Antonius T J; Sikorski, Pawel

2009-09-22

Droplet-based microfluidic systems are an expansion of the lab on a chip concept toward flexible, reconfigurable setups based on the modification and analysis of individual droplets. Superhydrophobic surfaces are one suitable candidate for the realization of droplet-based microfluidic systems as the high mobility of aqueous liquids on such surfaces offers possibilities to use novel or more efficient approaches to droplet movement. Here, copper-based superhydrophobic surfaces were produced either by the etching of polycrystalline copper samples along the grain boundaries using etchants common in the microelectronics industry, by electrodeposition of copper films with subsequent nanowire decoration based on thermal oxidization, or by a combination of both. The surfaces could be easily hydrophobized with thiol-modified fluorocarbons, after which the produced surfaces showed a water contact angle as high as 171 degrees +/- 2 degrees . As copper was chosen as the base material, established patterning techniques adopted from printed circuit board fabrication could be used to fabricate macrostructures on the surfaces with the intention to confine the droplets and, thus, to reduce the system's sensitivity to tilting and vibrations. A simple droplet-based microfluidic chip with inlets, outlets, sample storage, and mixing areas was produced. Wire guidance, a relatively new actuation method applicable to aqueous liquids on superhydrophobic surfaces, was applied to move the droplets.

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

PubMed

Gao, Detian; Back, Thomas G

2012-11-12

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

The Simultaneous Electrochemical Detection of Catechol and Hydroquinone with [Cu(Sal-β-Ala)(3,5-DMPz)2]/SWCNTs/GCE

PubMed Central

Alshahrani, Lina Abdullah; Li, Xi; Luo, Hui; Yang, Linlin; Wang, Mengmeng; Yan, Songling; Liu, Peng; Yang, Yuqin; Li, Quanhua

2014-01-01

A glassy carbon electrode was modified with a copper(II) complex [Cu(Sal-β-Ala) (3,5-DMPz)2] (Sal = salicylaldehyde, β-Ala = β-alanine, 3,5-DMPz = 3,5-dimethylpyrazole) and single-walled carbon nanotubes (SWCNTs). The modified electrode was used to detect catechol (CT) and hydroquinone (HQ) and exhibited good electrocatalytic activities toward the oxidation of CT and HQ. The peak currents were linear with the CT and HQ concentrations over the range of 5–215 μmol·L−1 and 5–370 μmol·L−1 with corresponding detection limits of 3.5 μmol·L−1 and 1.46 μmol·L−1 (S/N = 3) respectively. Moreover, the modified electrode exhibited good sensitivity, stability and reproducibility for the determination of CT and HQ, indicating the promising applications of the modified electrode in real sample analysis. PMID:25429411

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

Synthesis of copper oxide nanowires and nanoporous copper via environmentally friendly transformation of bulk copper-calcium alloys.

PubMed

Zhang, X; Turcheniuk, K; Zusmann, B; Benson, J; Nelson, S; Luo, S; Magasinski, A; Yushin, G

2018-05-24

In this work, we report a novel, one-step, inexpensive and environmentally friendly synthesis of Cu nanostructures by means of chemical de-alloying of bulk Cu-Ca alloys in aqueous solutions. By controlling the synthesis conditions, we tune the morphology of the nanostructured Cu from nanoporous Cu to copper oxide nanowires.

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2012 CFR

2012-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2013 CFR

2013-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

A Novel Anti-Influenza Copper Oxide Containing Respiratory Face Mask

PubMed Central

Borkow, Gadi; Zhou, Steve S.; Page, Tom; Gabbay, Jeffrey

2010-01-01

Background Protective respiratory face masks protect the nose and mouth of the wearer from vapor drops carrying viruses or other infectious pathogens. However, incorrect use and disposal may actually increase the risk of pathogen transmission, rather than reduce it, especially when masks are used by non-professionals such as the lay public. Copper oxide displays potent antiviral properties. A platform technology has been developed that permanently introduces copper oxide into polymeric materials, conferring them with potent biocidal properties. Methodology/Principal Findings We demonstrate that impregnation of copper oxide into respiratory protective face masks endows them with potent biocidal properties in addition to their inherent filtration properties. Both control and copper oxide impregnated masks filtered above 99.85% of aerosolized viruses when challenged with 5.66±0.51 and 6.17±0.37 log10TCID50 of human influenza A virus (H1N1) and avian influenza virus (H9N2), respectively, under simulated breathing conditions (28.3 L/min). Importantly, no infectious human influenza A viral titers were recovered from the copper oxide containing masks within 30 minutes (≤0.88 log10TCID50), while 4.67±1.35 log10TCID50 were recovered from the control masks. Similarly, the infectious avian influenza titers recovered from the copper oxide containing masks were ≤0.97±0.01 log10TCID50 and from the control masks 5.03±0.54 log10TCID50. The copper oxide containing masks successfully passed Bacterial Filtration Efficacy, Differential Pressure, Latex Particle Challenge, and Resistance to Penetration by Synthetic Blood tests designed to test the filtration properties of face masks in accordance with the European EN 14683:2005 and NIOSH N95 standards. Conclusions/Significance Impregnation of copper oxide into respiratory protective face masks endows them with potent anti-influenza biocidal properties without altering their physical barrier properties. The use of biocidal masks may significantly reduce the risk of hand or environmental contamination, and thereby subsequent infection, due to improper handling and disposal of the masks. PMID:20592763

Electrochemical properties and electrocatalytic activity of conducting polymer/copper nanoparticles supported on reduced graphene oxide composite

NASA Astrophysics Data System (ADS)

Ehsani, Ali; Jaleh, Babak; Nasrollahzadeh, Mahmoud

2014-07-01

Reduced graphene oxide (rGO) was used to support Cu nanoparticles. As electro-active electrodes for supercapacitors composites of reduced graphene oxide/Cu nanoparticles (rGO/CuNPs) and polytyramine (PT) with good uniformity are prepared by electropolymerization. Composite of rGO/CuNPs-PT was synthesized by cyclic voltammetry (CV) methods and electrochemical properties of film were investigated by using electrochemical techniques. The results show that, the rGO/CuNPs-PT/G has better capacitance performance. This is mainly because of the really large surface area and the better electronic and ionic conductivity of rGO/CuNPs-PT/G, which lead to greater double-layer capacitance and faradic pseudo capacitance. Modified graphite electrodes (rGO/CuNPs-PT/G) were examined for their redox process and electrocatalytic activities towards the oxidation of methanol in alkaline solutions. The methods of cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) were employed. In comparison with a Cu-PT/G (Graphite), rGO/CuNPs-PT/G modified electrode shows a significantly higher response for methanol oxidation. A mechanism based on the electro-chemical generation of Cu(III) active sites and their subsequent consumptions by methanol have been discussed.

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

PubMed

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

2014-01-01

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

Change of brown coal oxidation kinetic characteristics by promoting additives appending in the form of copper salts

NASA Astrophysics Data System (ADS)

Larionov, K. B.; Mishakov, I. V.; Gromov, A. A.; Zenkov, A. V.

2017-11-01

Process of brown coal oxidation with 5%wt content of copper-salt additives of various nature (Cu (NO3)2, CuSO4 and Cu(CH3COO)2) was studied. The experiment has been performed by thermogravimetric analysis at a heating rate of 2.5°C/min to a maximum temperature of 600°C in the air. Analytical evaluation of oxidation process kinetic characteristics has been conducted based on the results of TGA. It has been established that addition of initiating agents leads to significant reduction in the initial ignition temperature of coal (ΔTi = 15÷40°C), shortening of the sample warm-up time to the ignition point (Δte = 6÷12 min) and reduction of the sample burning time (Δtf = 40÷54 min). The following series of additives activity affecting ignition temperature of coals has been established: Cu(CH3COO)2 > Cu(NO3)2 > CuSO4. Additionally, the opposite can be said about the effect of additives on residence time of the sample in its combustion area (CuSO4 > Cu(NO3)2 > Cu(CH3COO)2). According to mass spectrometric analysis, presence of NOx, SO2, CO2 (intense peaks at 190÷290°C) was recorded in oxidation products of modified samples, which is explained by partial or complete decomposition of salts.

Transpassive Dissolution of Copper and Rapid Formation of Brilliant Colored Copper Oxide Films

NASA Astrophysics Data System (ADS)

Fredj, Narjes; Burleigh, T. David; New Mexico Tech Team

2014-03-01

This investigation describes an electrochemical technique for growing adhesive copper oxide films on copper with attractive colors ranging from gold-brown to pearl with intermediate colors from red violet to gold green. The technique consists of anodically dissolving copper at transpassive potentials in hot sodium hydroxide, and then depositing brilliant color films of Cu2O onto the surface of copper after the anodic potential has been turned off. The color of the copper oxide film depends on the temperature, the anodic potential, the time t1 of polarization, and the time t2, which is the time of immersion after potential has been turned off. The brilliant colored films were characterized using glancing angle x-ray diffraction, and the film was found to be primarily Cu2O. Cyclic voltammetry, chronopotentiometry, scanning electron microscopy, and x-ray photoelectron spectroscopy were also used to characterize these films.

Gastrointestinal effects associated with soluble and insoluble copper in drinking water.

PubMed Central

Pizarro, F; Olivares, M; Araya, M; Gidi, V; Uauy, R

2001-01-01

The aim of this study was to determine whether total copper or soluble copper concentration is associated with gastrointestinal signs and symptoms. Forty-five healthy adult women (18-55 years of age), living in Santiago, Chile, ingested tap water with 5 mg/L of copper containing different ratios of soluble copper (copper sulfate) and insoluble copper (copper oxide) over a 9-week period. Three randomized sequences of the different copper ratios (0:5, 1:4, 2:3, 3:2, and 5:0 mg/L) were followed. Subjects recorded their water consumption and gastrointestinal symptoms daily on a special form. Mean water consumption was similar among groups. Serum copper levels, ceruloplasmin, and activities of liver enzymes were within normal limits. No differences were detected between the means of biochemical parameters at the beginning and at the end of the study. Twenty subjects presented gastrointestinal disturbances at least once during the study, 9 suffered diarrhea (with or without abdominal pain and vomiting), and the other 11 subjects reported abdominal pain, nausea, or vomiting. No differences were found in incidence of abdominal pain, nausea, vomiting, and diarrhea regardless of the ratio of copper sulfate to copper oxide. In conclusion, both copper sulfate (a soluble compound) and copper oxide (an insoluble compound) have comparable effects on the induction of gastrointestinal manifestations, implying that similar levels of ionic copper were present in the stomach. PMID:11673125

Photocatalytic water splitting over titania supported copper and nickel oxide in photoelectrochemical cell; optimization of photoconversion efficiency

NASA Astrophysics Data System (ADS)

Muti Mohamed, Norani; Bashiri, Robabeh; Kait, Chong Fai; Sufian, Suriati

2018-04-01

we investigated the influence of fluctuating the preparation variables of TiO2 on the efficiency of photocatalytic water splitting in photoelectrochemical (PEC) cell. Hydrothermal associated sol-gel technique was applied to synthesis modified TiO2 with nickel and copper oxide. The variation of water (mL), acid (mL) and total metal loading (%) were mathematically modelled using central composite design (CCD) from the response surface method (RSM) to explore the single and combined effects of parameters on the system performance. The experimental data were fitted using quadratic polynomial regression model from analysis of variance (ANOVA). The coefficient of determination value of 98% confirms the linear relationship between the experimental and predicted values. The amount of water had maximum effect on the photoconversion efficiency due to a direct effect on the crystalline and the number of defects on the surface of photocatalyst. The optimal parameter ratios with maximum photoconversion efficiency were 16 mL, 3 mL and 5 % for water, acid and total metal loading, respectively.

In situ spectroscopic monitoring of CO2 reduction at copper oxide electrode.

PubMed

Wang, Liying; Gupta, Kalyani; Goodall, Josephine B M; Darr, Jawwad A; Holt, Katherine B

2017-04-28

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO 3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(i) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO 2 saturated KHCO 3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO 2 . On cycling to negative potentials, larger reduction currents were observed in the presence of CO 2 ; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO 2 CuO underwent reduction to Cu 2 O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials.

Ethanol exposure induces oxidative stress and impairs nitric oxide availability in the human placental villi: a possible mechanism of toxicity.

PubMed

Kay, H H; Grindle, K M; Magness, R R

2000-03-01

We undertook this investigation to explore the effects of ethanol exposure on nitric oxide synthase levels and nitric oxide release. Our hypothesis was that ethanol exposure modifies nitric oxide activity within the placenta as a result of oxidative stress. Four 10-g samples of term normal human placental villous tissue were perifused with nonrecirculating Dulbecco's modified Eagle's medium and 25-mmol/L N-[2-hydroxyethyl]piperazine-N'-[2-ethanesulfonic acid] with 0-, 50-, 100-, or 200-mmol/L ethanol. After 2 hours of exposure, tissue was removed, fixed, and frozen for analysis. Immunohistochemical analysis was performed for subtype I or neuronal nitric oxide synthase (nNOS), subtype II or inducible nitric oxide synthase (iNOS), and subtype III or endothelial nitric oxide synthase (eNOS) localization. Western blot analysis was performed for eNOS quantitation. Cyclic guanosine monophosphate and copper-zinc superoxide dismutase levels were measured by electroimmunoassay and kinetic assay, respectively. Nitric oxide release was analyzed by a Sievers nitric oxide analyzer. Immunohistochemical examination confirmed that only eNOS was localized to the syncytiotrophoblasts. After ethanol exposure, eNOS protein expression increased 2.5- to 3.0-fold over that of the control. Tissue cyclic guanosine monophosphate content and nitric oxide release into the effluent were decreased, whereas superoxide dismutase levels were increased at higher ethanol levels (P <.05). Ethanol exposure appears to induce oxidative stress, which may account for the decreased nitric oxide release, because nitric oxide may be shunted toward scavenging free radicals. Increased eNOS protein expression may be a response to the increased demand for nitric oxide. Decreased nitric oxide availability could adversely affect placental blood flow regulation, which could, in turn, account for the growth restriction seen in ethanol-exposed fetuses.

Synergistic interaction between oxides of copper and iron for production of fatty alcohols from fatty acids

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

Kandel, Kapil; Chaudhary, Umesh; Nelson, Nicholas C.

2015-10-08

In this study, the selective hydrogenation of fatty acids to fatty alcohols can be achieved under moderate conditions (180 °C, 30 bar H 2) by simultaneously supporting copper and iron oxides on mesoporous silica nanoparticles. The activity of the cosupported oxides is significantly higher than that of each supported metal oxide and of a physical mixture of both individually supported metal oxides. A strong interaction between both metal oxides is evident from dispersion, XRD, TPR, and acetic acid TPD measurements, which is likely responsible for the synergistic behavior of the catalyst. Copper oxide is reduced in situ to its metallicmore » form and thereby activates hydrogen.« less

CuO based catalysts on modified acidic silica supports tested in the de-NOx reduction.

PubMed

Bennici, Simona; Gervasini, Antonella; Lazzarin, Marta; Ragaini, Vittorio

2005-03-01

A series of dispersed CuO catalysts supported on modified silica supports with Al2O3 (SA), TiO2 (ST), and ZrO2 (SZ) were prepared optimising the adsorption method of copper deposition assisted by ultrasound treatment, already reported in a previous paper (S. Bennici, A. Gervasini, V. Ragaini, Ultrason. Sonochem. 10 (2003) 61). The obtained catalysts were characterized in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N2 adsorption, X-ray photoelectron spectroscopy, scanning electron microscopy) properties. The morphology of the finished materials was not deeply modified compared with that of the relevant supports. The employed complemented techniques evidenced a well dispersed CuO phase with a copper-support interaction on the most acidic supports (SA and SZ). The catalyst performances were studied in the reaction of selective catalytic reduction of NOx with ethene in oxidizing atmosphere in a flow apparatus under variable times (0.360-0.072 s) and temperatures (200-450 degrees C). The catalysts prepared on the most acidic supports (SA and SZ) were the most active and selective towards N2 formation. They showed a particular interesting activity in the reaction of NO2 reduction besides that of NO reduction.

The Variations of Glycolysis and TCA Cycle Intermediate Levels Grown in Iron and Copper Mediums of Trichoderma harzianum.

PubMed

Tavsan, Zehra; Ayar Kayali, Hulya

2015-05-01

The efficiency of optimal metabolic function by microorganism depends on various parameters, especially essential metal supplementation. In the present study, the effects of iron and copper metals on metabolism were investigated by determination of glycolysis and tricarboxylic acid (TCA) cycle metabolites' levels with respect to the metal concentrations and incubation period in Trichoderma harzianum. The pyruvate and citrate levels of T. harzianum increased up to 15 mg/L of copper via redirection of carbon flux though glycolysis by suppression of pentose phosphate pathway (PPP). However, the α-ketoglutarate levels decreased at concentration higher than 5 mg/L of copper to overcome damage of oxidative stress. The fumarate levels correlated with the α-ketoglutarate levels because of substrate limitation. Besides, in T. harzianum cells grown in various concentrations of iron-containing medium, the intracellular pyruvate, citrate, and α-ketoglutarate levels showed positive correlation with iron concentration due to modifying of expression of glycolysis and TCA cycle enzymes via a mechanism involving cofactor or allosteric regulation. However, as a result of consuming of prior substrates required for fumarate production, its levels rose up to 10 mg/L.

Change of Cu+ species and synergistic effect of copper and cerium during reduction-oxidation treatment for preferential CO oxidation

NASA Astrophysics Data System (ADS)

Zhang, Hao; Zhao, Xiaozhou; Wang, Shuang; Zeng, Shanghong; Su, Haiquan

2018-05-01

The CuO-CeO2@SiO2 catalyst with flower-sphere morphology was prepared by the impregnation method and then experienced the reduction-oxidation treatment at different temperatures. The multi-technique characterization shows that the reduction-oxidation treatment can remodel CuO, improve textural and surface properties and change Cu+ content and synergistic effect of copper and cerium. The importance of this work lies in the fact that the decrease of Cu+ content and synergistic effect of copper and cerium that occurs in the reduction-oxidation process results in the decrease of catalytic activity over the CuO-CeO2@SiO2 catalyst for preferential CO oxidation. The process of reaction in rich-hydrogen streams is equivalent to a reduction procedure which decreases Cu+ content and synergistic effect of copper and cerium.

Biosynthesis, characterization and antimicrobial activity of copper oxide nanoparticles (CONPs) produced using brown alga extract ( Bifurcaria bifurcata)

NASA Astrophysics Data System (ADS)

Abboud, Y.; Saffaj, T.; Chagraoui, A.; El Bouari, A.; Brouzi, K.; Tanane, O.; Ihssane, B.

2014-06-01

Recently, biosynthesis of nanoparticles has attracted scientists' attention because of the necessity to develop new clean, cost-effective and efficient synthesis techniques. In particular, metal oxide nanoparticles are receiving increasing attention in a large variety of applications. However, up to now, the reports on the biopreparation and characterization of nanocrystalline copper oxide are relatively few compared to some other metal oxides. In this paper, we report for the first time the use of brown alga ( Bifurcaria bifurcata) in the biosynthesis of copper oxide nanoparticles of dimensions 5-45 nm. The synthesized nanomaterial is characterized by UV-visible absorption spectroscopy and Fourier transform infrared spectrum analysis. X-ray diffraction confirms the formation and the crystalline nature of copper oxide nanomaterial. Further, these nanoparticles were found to exhibit high antibacterial activity against two different strains of bacteria Enterobacter aerogenes (Gram negative) and Staphylococcus aureus (Gram positive).

Auger electron spectroscopy study of initial stages of oxidation in a copper - 19.6-atomic-percent-aluminum alloy

NASA Technical Reports Server (NTRS)

Ferrante, J.

1973-01-01

Auger electron spectroscopy was used to examine the initial stages of oxidation of a polycrystalline copper - 19.6 a/o-aluminum alloy. The growth of the 55-eV aluminum oxide peak and the decay of the 59-, 62-, and 937-eV copper peaks were examined as functions of temperature, exposure, and pressure. Pressures ranged from 1x10 to the minus 7th power to 0.0005 torr of O2. Temperatures ranged from room temperature to 700 C. A completely aluminum oxide surface layer was obtained in all cases. Complete disappearance of the underlying 937-eV copper peak was obtained by heating at 700 C in O2 at 0.0005 torr for 1 hr. Temperature studies indicated that thermally activated diffusion was important to the oxidation studies. The initial stages of oxidation followed a logarithmic growth curve.

Copper Doping of Zinc Oxide by Nuclear Transmutation

DTIC Science & Technology

2014-03-27

Copper Doping of Zinc Oxide by Nuclear Transmutation THESIS Matthew C. Recker, Captain, USAF AFIT-ENP-14-M-30 DEPARTMENT OF THE AIR FORCE AIR...NUCLEAR TRANSMUTATION THESIS Presented to the Faculty Department of Engineering Physics Graduate School of Engineering and Management Air Force...COPPER DOPING OF ZINC OXIDE BY NUCLEAR TRANSMUTATION Matthew C. Recker, BS Captain, USAF Approved: //signed// 27 February 2014 John W. McClory, PhD

The oxidation of copper catalysts during ethylene epoxidation.

PubMed

Greiner, M T; Jones, T E; Johnson, B E; Rocha, T C R; Wang, Z J; Armbrüster, M; Willinger, M; Knop-Gericke, A; Schlögl, R

2015-10-14

The oxidation of copper catalysts during ethylene epoxidation was characterized using in situ photoemission spectroscopy and electron microscopy. Gas chromatography, proton-transfer reaction mass spectrometry and electron-ionization mass spectrometry were used to characterize the catalytic properties of the oxidized copper. We find that copper corrodes during epoxidation in a 1 : 1 mixture of oxygen and ethylene. The catalyst corrosion passes through several stages, beginning with the formation of an O-terminated surface, followed by the formation of Cu2O scale and eventually a CuO scale. The oxidized catalyst exhibits measurable activity for ethylene epoxidation, but with a low selectivity of <3%. Tests on pure Cu2O and CuO powders confirm that the oxides intrinsically exhibit partial-oxidation activity. Cu2O was found to form acetaldehyde and ethylene epoxide in roughly equal amounts (1.0% and 1.2% respectively), while CuO was found to form much less ethyl aldehyde than ethylene epoxide (0.1% and 1.0%, respectively). Metallic copper catalysts were examined in extreme dilute-O2 epoxidation conditions to try and keep the catalyst from oxidizing during the reaction. It was found that in feed of 1 part O2 to 2500 parts C2H4 (PO2 = 1.2 × 10(-4) mbar) the copper surface becomes O-terminated. The O-terminated surface was found to exhibit partial-oxidation selectivity similar to that of Cu2O. With increasing O2 concentration (>8/2500) Cu2O forms and eventually covers the surface.

Copper Complex in Poly(vinyl chloride) as a Nitric Oxide-Generating Catalyst for the Control of Nitrifying Bacterial Biofilms.

PubMed

Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

2015-10-14

In this study, catalytic generation of nitric oxide by a copper(II) complex embedded within a poly(vinyl chloride) matrix in the presence of nitrite (source of nitric oxide) and ascorbic acid (reducing agent) was shown to effectively control the formation and dispersion of nitrifying bacteria biofilms. Amperometric measurements indicated increased and prolonged generation of nitric oxide with the addition of the copper complex when compared to that with nitrite and ascorbic acid alone. The effectiveness of the copper complex-nitrite-ascorbic acid system for biofilm control was quantified using protein analysis, which showed enhanced biofilm suppression when the copper complex was used in comparison to that with nitrite and ascorbic acid treatment alone. Confocal laser scanning microscopy (CLSM) and LIVE/DEAD staining revealed a reduction in cell surface coverage without a loss of viability with the copper complex and up to 5 mM of nitrite and ascorbic acid, suggesting that the nitric oxide generated from the system inhibits proliferation of the cells on surfaces. Induction of nitric oxide production by the copper complex system also triggered the dispersal of pre-established biofilms. However, the addition of a high concentration of nitrite and ascorbic acid to a pre-established biofilm induced bacterial membrane damage and strongly decreased the metabolic activity of planktonic and biofilm cells, as revealed by CLSM with LIVE/DEAD staining and intracellular adenosine triphosphate measurements, respectively. This study highlights the utility of the catalytic generation of nitric oxide for the long-term suppression and removal of nitrifying bacterial biofilms.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Influence of gold content on copper oxidation from silver-gold-copper alloys

NASA Astrophysics Data System (ADS)

Swinbourne, D. R.; Barbante, G. G.; Strahan, A.

1996-10-01

In the final stages of the smelting of copper anode slimes, a silver alloy, known as “doré,” is produced. Oxidation refining is used to remove copper since this element interferes with subsequent electroparting of the small amounts of gold and platinum group metals in the doré. The gold content of doré can be greatly increased by gold scrap additions and this may affect the minimum achievable copper content of doré. In this work, silver-gold-copper alloys were oxidized by injecting pure oxygen at 1100 °C in the absence of any slag cover. For the gold contents expected in practice, the equilibrium copper content of the doré did not increase significantly as the gold content increased. However, at the other extreme of composition, the equilibrium copper content was a very strong function of the silver content of the gold bullion. The activity coefficient of copper in silver-gold alloys was calculated and compared to those predicted from a ternary subregular solution model of the system Ag-Au-Cu. Satisfactory agreement was found.

Biological and Environmental Transformations of Copper-Based Nanomaterials

PubMed Central

Wang, Zhongying; Von Dem Bussche, Annette; Kabadi, Pranita K.; Kane, Agnes B.; Hurt, Robert H.

2013-01-01

Copper-based nanoparticles are an important class of materials with applications as catalysts, conductive inks, and antimicrobial agents. Environmental and safety issues are particularly important for copper-based nanomaterials because of their potential large-scale use and their high redox activity and toxicity reported from in vitro studies. Elemental nanocopper oxidizes readily upon atmospheric exposure during storage and use, so copper oxides are highly relevant phases to consider in studies of environmental and health impacts. Here we show that copper oxide nanoparticles undergo profound chemical transformations under conditions relevant to living systems and the natural environment. Copper oxide nanoparticle (CuO-NP) dissolution occurs at lysosomal pH (4-5), but not at neutral pH in pure water. Despite the near-neutral pH of cell culture medium, CuO-NPs undergo significant dissolution in media over time scales relevant to toxicity testing due to ligand-assisted ion release, in which amino acid complexation is an important contributor. Electron paramagnetic resonance (EPR) spectroscopy shows that dissolved copper in association with CuO-NPs are the primary redox-active species. CuO-NPs also undergo sulfidation by a dissolution-reprecipitation mechanism, and the new sulfide surfaces act as catalysts for sulfide oxidation. Copper sulfide NPs are found to be much less cytotoxic than CuO NPs, which is consistent with the very low solubility of CuS. Despite this low solubility of CuS, EPR studies show that sulfidated CuO continues to generate some ROS activity due to the release of free copper by H2O2 oxidation during the Fenton-chemistry-based EPR assay. While sulfidation can serve as a natural detoxification process for nanosilver and other chalcophile metals, our results suggest that sulfidation may not fully and permanently detoxify copper in biological or environmental compartments that contain reactive oxygen species. PMID:24032665

Selective catalytic reduction of nitrogen oxides over a modified silicoaluminophosphate commercial zeolite.

PubMed

Petitto, Carolina; Delahay, Gérard

2018-03-01

Nitrogen oxides (NO x : NO, NO 2 ) are a concern due to their adverse health effects. Diesel engine transport sector is the major emitter of NO x . The regulations have been strengthened and to comply with them, one of the two methods commonly used is the selective catalytic reduction of NO x by NH 3 (NH 3 -SCR), NH 3 being supplied by the in-situ hydrolysis of urea. Efficiency and durability of the catalyst for this process are highly required. Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800°C. In this study, very active catalysts for the NH 3 -SCR of NO x were prepared by using a silicoaluminophosphate commercial zeolite as copper host structure. Characterizations by X-ray diffraction (XRD), scanning electron microscopy (SEM) and temperature programmed desorption of ammonia (NH 3 -TPD) showed that this commercial zeolite was hydrothermally stable up to 850°C and, was able to retain some structural properties up to 950°C. After hydrothermal treatment at 850°C, the NO x reduction efficiency into NH 3 -SCR depends on the copper content. The catalyst with a copper content of 1.25wt.% was the most active. The difference in activity was much more important when using NO than the fast NO/NO 2 reaction mixture. Copyright © 2017. Published by Elsevier B.V.

Role of copper oxides in contact killing of bacteria.

PubMed

Hans, Michael; Erbe, Andreas; Mathews, Salima; Chen, Ying; Solioz, Marc; Mücklich, Frank

2013-12-31

The potential of metallic copper as an intrinsically antibacterial material is gaining increasing attention in the face of growing antibiotics resistance of bacteria. However, the mechanism of the so-called "contact killing" of bacteria by copper surfaces is poorly understood and requires further investigation. In particular, the influences of bacteria-metal interaction, media composition, and copper surface chemistry on contact killing are not fully understood. In this study, copper oxide formation on copper during standard antimicrobial testing was measured in situ by spectroscopic ellipsometry. In parallel, contact killing under these conditions was assessed with bacteria in phosphate buffered saline (PBS) or Tris-Cl. For comparison, defined Cu2O and CuO layers were thermally generated and characterized by grazing incidence X-ray diffraction. The antibacterial properties of these copper oxides were tested under the conditions used above. Finally, copper ion release was recorded for both buffer systems by inductively coupled plasma atomic absorption spectroscopy, and exposed copper samples were analyzed for topographical surface alterations. It was found that there was a fairly even growth of CuO under wet plating conditions, reaching 4-10 nm in 300 min, but no measurable Cu2O was formed during this time. CuO was found to significantly inhibit contact killing, compared to pure copper. In contrast, thermally generated Cu2O was essentially as effective in contact killing as pure copper. Copper ion release from the different surfaces roughly correlated with their antibacterial efficacy and was highest for pure copper, followed by Cu2O and CuO. Tris-Cl induced a 10-50-fold faster copper ion release compared to PBS. Since the Cu2O that primarily forms on copper under ambient conditions is as active in contact killing as pure copper, antimicrobial objects will retain their antimicrobial properties even after oxide formation.

Oxidation Behavior of Copper Alloy Candidates for Rocket Engine Applications (Technical Poster)

NASA Technical Reports Server (NTRS)

Ogbuji, Linus U. J.; Humphrey, Donald H.; Barrett, Charles A.; Greenbauer-Seng, Leslie (Technical Monitor); Gray, Hugh R. (Technical Monitor)

2002-01-01

A rocket engine's combustion chamber is lined with material that is highly conductive to heat in order to dissipate the huge thermal load (evident in a white-hot exhaust plume). Because of its thermal conductivity copper is the best choice of liner material. However, the mechanical properties of pure copper are inadequate to withstand the high stresses, hence, copper alloys are needed in this application. But copper and its alloys are prone to oxidation and related damage, especially "blanching" (an oxidation-reduction mode of degradation). The space shuttle main engine combustion chamber is lined with a Cu-Ag-Zr alloy, "NARloy-Z", which exhibits blanching. A superior liner is being sought for the next generation of RLVs (Reusable Launch Vehicles) It should have improved mechanical properties and higher resistance to oxidation and blanching, but without substantial penalty in thermal conductivity. GRCop84, a Cu-8Cr-4Nb alloy (Cr2Nb in Cu matrix), developed by NASA Glenn Research Center (GRC) and Case Western Reserve University, is a prime contender for RLV liner material. In this study, the oxidation resistance of GRCop-84 and other related/candidate copper alloys are investigated and compared

A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

NASA Technical Reports Server (NTRS)

Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

1980-01-01

The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

Electrical Characterization of Spherical Copper Oxide Memristive Array Sensors

DTIC Science & Technology

2014-03-27

Quartz Tube Furnace . . . . . . . 37 3.3.2.2 Thermal Oxidation in Air on a Hot Plate . . . . . . . . . 38 3.4 Experimental Setup for Electrical...closed hot plate . . . 80 B.1 Oxidation rates for copper at 100 °C by two different formulas . . . . . . . . . 81 xi List of Tables Table Page 2.1 The... Tectonics Inc. and manufactured by Canfield Technologies using a proprietary fabrication method. As received, the copper spheres may have contaminants

Assessing the electrochemical performance of a supercapacitor electrode made of copper oxide and activated carbon using liquid phase plasma

NASA Astrophysics Data System (ADS)

Ki, Seo Jin; Lee, Heon; Park, Young-Kwon; Kim, Sun-Jae; An, Kay-Hyeok; Jung, Sang-Chul

2018-07-01

Successful modification of surface properties of a nanocomposite electrode is prerequisite to enhancing the overall performance of electrochemical supercapacitors. The present study was designed to describe the microstructural and electrochemical characteristics of a new composite electrode assembled by activated carbon (AC) powder (as a host) and copper precursor (as a guest) using liquid phase plasma. The fabrication processes were conducted by changing plasma discharge time from 30 to 90 min in the presence and absence of (thermal) oxidation. We observed that merging plasma and oxidation treatments raised the content of copper oxide nanoparticles precipitated (evenly) on the AC surface, along with oxygen. A mixed valence state of copper oxides (in the forms of Cuo, Cu2O, and CuO) was found in different composites with and without oxidation, where CuO and Cuo affected a specific capacitance in positive and negative ways, respectively. This led to the difference of electrochemical stability and resistance among the assembled composites. For instance, the best cycling performance was observed in the plasma-treated composite for 90 min with oxidation, whereas that of 60 min without oxidation recorded the lowest resistance. Therefore, a proper balance between the capacitance and resistance appears to be required for effective fabrication of the supercapacitor electrode, specifically in cases involving copper oxides.

Lead-Free Double-Base Propellant for the 2.75 Inch Rocket Motor

NASA Technical Reports Server (NTRS)

Magill, B. T.; Nauflett, G. W.; Furrow, K. W.

2000-01-01

The current MK 66 2.75 inch Rocket Motor double-base propellant contains the lead-based ballistic modifier LC-12-15 to achieve the desired plateau and mesa burning rate characteristics. The use of lead compounds poses a concern for the environment and for personal safety due to the metal's toxic nature when introduced into the atmosphere by propellant manufacture, rocket motor firing, and disposal. Copper beta-resorcylate (copper 2,4-di-hydroxy-benzoate) was successfully used in propellant as a simple modifier in the mid 1970's. This and other compounds have also been mixed with lead salts to obtain more beneficial ballistic results. Synthesized complexes of lead and copper compounds soon replaced the mixtures. The complexes incorporate the lead, copper lack of organic liquids, which allows for easier propellant processing. About ten years ago, the Indian Head Division, Naval Surface Warfare Center (NSWC), initiated an effort to develop a lead-free propellant for use in missile systems. Several lead-free propellant candidate formulations were developed. About five years ago, NSWC, in conjunction with Alliant Techsystems, Radford Army Ammunition Plant, continued ballistic modifier investigations. A four component ballistic modifier system without lead for double-base propellants that provide adequate plateau and mesa burn rate characteristics was developed and patented. The ballistic modifier's system contains bismuth subsalicylate, 1.5 percent; copper salicylate, 1.0 percent, copper stannate, 0.77 percent; and carbon black, 0.1 percent. Action time and impulse data obtained through multiple static firings indicate that the new lead-free double-base propellant, while not a match for NOSIH-AA-2, will be a very suitable replacement in the 2.75 inch Rocket Motor. Accelerated aging of the double-base propellant containing the lead-free ballistic modifier showed that it had a much higher rate of stabilizer depletion than the AA-2. A comprehensive study showed that an increased rate of stabilizer depletion occurred in propellants containing monobasic copper salicylate. The study also showed that propellants containing a mixture of bismuth subsalicylate and copper salicylate, had only about one-half the stabilizer depletion rate than those with copper salicylate alone. The copper salicylate catalyzes the decomposition of nitroglycerin, which triggers a chain of events leading to the increased rate of stabilizer depletion. A program has been initiated to coat the ballistic modifier, thus isolating it from the nitroglycerin.

Virtual electrochemical nitric oxide analyzer using copper, zinc superoxide dismutase immobilized on carbon nanotubes in polypyrrole matrix.

PubMed

Madasamy, Thangamuthu; Pandiaraj, Manickam; Balamurugan, Murugesan; Karnewar, Santosh; Benjamin, Alby Robson; Venkatesh, Krishna Arun; Vairamani, Kanagavel; Kotamraju, Srigiridhar; Karunakaran, Chandran

2012-10-15

In this work, we have designed and developed a novel and cost effective virtual electrochemical analyzer for the measurement of NO in exhaled breath and from hydrogen peroxide stimulated endothelial cells using home-made potentiostat. Here, data acquisition system (NI MyDAQ) was used to acquire the data from the electrochemical oxidation of NO mediated by copper, zinc superoxide dismutase (Cu,ZnSOD). The electrochemical control programs (graphical user-interface software) were developed using LabVIEW 10.0 to sweep the potential, acquire the current response and process the acquired current signal. The Cu,ZnSOD (SOD1) immobilized on the carbon nanotubes in polypyrrole modified platinum electrode was used as the NO biosensor. The electrochemical behavior of the SOD1 modified electrode exhibited the characteristic quasi-reversible redox peak at the potential, +0.06 V vs. Ag/AgCl. The biological interferences were eliminated by nafion coated SOD1 electrode and then NO was measured selectively. Further, this biosensor showed a wide linear range of response over the concentration of NO from 0.1 μM to 1 mM with a detection limit of 0.1 μM and high sensitivity of 1.1 μA μM(-1). The electroanalytical results obtained here using the developed virtual electrochemical instrument were also compared with the standard cyclic voltammetry instrument and found in agreement with each other. Copyright © 2012 Elsevier B.V. All rights reserved.

Cyclic voltammetry deposition of copper nanostructure on MWCNTs modified pencil graphite electrode: An ultra-sensitive hydrazine sensor.

PubMed

Heydari, Hamid; Gholivand, Mohammad B; Abdolmaleki, Abbas

2016-09-01

In this study, Copper (Cu) nanostructures (CuNS) were electrochemically deposited on a film of multiwall carbon nanotubes (MWCNTs) modified pencil graphite electrode (MWCNTs/PGE) by cyclic voltammetry method to fabricate a CuNS-MWCNTs composite sensor (CuNS-MWCNT/PGE) for hydrazine detection. Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectroscopy (EDX) were used for the characterization of CuNS on the MWCNTs matrix. The composite of CuNS-MWCNTs was characterized with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The preliminary studies showed that the proposed sensor have a synergistic electrocatalytic activity for the oxidation of hydrazine in phosphate buffer. The catalytic currents of square wave voltammetry had a linear correlation with the hydrazine concentration in the range of 0.1 to 800μM with a low detection limit of 70nM. Moreover, the amperometric oxidation current exhibited a linear correlation with hydrazine concentration in the concentration range of 50-800μM with the detection limit of 4.3μM. The proposed electrode was used for the determination of hydrazine in real samples and the results were promising. Empirical results also indicated that the sensor had good reproducibility, long-term stability, and the response of the sensor to hydrazine was free from interferences. Moreover, the proposed sensor benefits from simple preparation, low cost, outstanding sensitivity, selectivity, and reproducibility for hydrazine determination. Copyright © 2016. Published by Elsevier B.V.

Stage specific effects of soluble copper and copper oxide nanoparticles during sea urchin embryo development and their relation to intracellular copper uptake.

PubMed

Torres-Duarte, Cristina; Ramos-Torres, Karla M; Rahimoff, René; Cherr, Gary N

2017-08-01

The effects of exposure to either soluble copper (copper sulfate) or copper oxide nanoparticles (nano-CuO) during specific early developmental stages of sea urchin embryos were analyzed. Soluble copper caused significant malformations in embryos (skeletal malformations, delayed development or gut malformations) when present at any given stage, while cleavage stage was the most sensitive to nano-CuO exposure causing skeletal malformations and decreased total antioxidant capacity. The stage specificity was linked to higher endocytic activity during the first hours of development that leads to higher accumulation of copper in specific cells critical for development. Results indicate that nano-CuO results in higher accumulation of copper inside of embryos and this intracellular copper is more persistent as compared to soluble copper. The possible implications later in development are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Aberrant expression of copper associated genes after copper accumulation in COMMD1-deficient dogs.

PubMed

Favier, Robert P; Spee, Bart; Fieten, Hille; van den Ingh, Ted S G A M; Schotanus, Baukje A; Brinkhof, Bas; Rothuizen, Jan; Penning, Louis C

2015-01-01

COMMD1-deficient dogs progressively develop copper-induced chronic hepatitis. Since high copper leads to oxidative damage, we measured copper metabolism and oxidative stress related gene products during development of the disease. Five COMMD1-deficient dogs were studied from 6 months of age over a period of five years. Every 6 months blood was analysed and liver biopsies were taken for routine histological evaluation (grading of hepatitis), rubeanic acid copper staining and quantitative copper analysis. Expression of genes involved in copper metabolism (COX17, CCS, ATOX1, MT1A, CP, ATP7A, ATP7B, ) and oxidative stress (SOD1, catalase, GPX1 ) was measured by qPCR. Due to a sudden death of two animals, the remaining three dogs were treated with d-penicillamine from 43 months of age till the end of the study. Presented data for time points 48, 54, and 60 months was descriptive only. A progressive trend from slight to marked hepatitis was observed at histology, which was clearly preceded by an increase in semi-quantitative copper levels starting at 12 months until 42 months of age. During the progression of hepatitis most gene products measured were transiently increased. Most prominent was the rapid increase in the copper binding gene product MT1A mRNA levels. This was followed by a transient increase in ATP7A and ATP7B mRNA levels. In the sequence of events, copper accumulation induced progressive hepatitis followed by a transient increase in gene products associated with intracellular copper trafficking and temporal activation of anti-oxidative stress mechanisms. Copyright © 2014 Elsevier GmbH. All rights reserved.

Superconducting structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2003-04-01

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Superconducting Structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2005-09-13

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Mechanical Properties of Oxide Films on Electrolytic In-process Dressing (ELID) Copper-based Grinding Wheel

NASA Astrophysics Data System (ADS)

Kuai, J. C.; Wang, J. W.; Jiang, C. R.; Zhang, H. L.; Yang, Z. B.

2018-05-01

The mechanical properties of oxide films on copper based grinding wheel were studied by nanoindentation technique. The analysis of load displacement shows that the creep phenomenon occurs during the loading stage. Results show that the oxide film and the matrix have different characteristics, and the rigidity of the copper based grinding wheel is 0.6-1.3mN/nm, which is weaker than that of the matrix; the hardness of the oxide film is 2000-2300MPa, which is higher than the matrix; and the elastic modulus of the oxide film is 100-120GPa, also higher than the matrix.

Flavonoids-induced redox cycling of copper ions leads to generation of reactive oxygen species: A potential role in cancer chemoprevention.

PubMed

Arif, Hussain; Sohail, Aamir; Farhan, Mohd; Rehman, Ahmed Abdur; Ahmad, Aamir; Hadi, S M

2018-01-01

Flavonoids, a class of polyphenols are known to be effective inducers of apoptosis and cytotoxicity in cancer cells. It is believed that antioxidant activity of polyphenols cannot fully account for induction of apoptosis and chemotherapeutic prevention in various cancers. In this article, by employing single cell alkaline gel electrophoresis (comet assay), we established that antioxidants, flavonoids such as (myricetin=MN, fisetin=FN, quercetin=QN, kaempferol=KL and galangin=GN) can cause cellular DNA breakage, also act as pro-oxidant in presence of transition metal ion such as copper. It was observed that the extent of cellular DNA breakage was found significantly higher in presence of copper. Hydroxyl radicals are generated as a sign of flavonoids' pro-oxidant nature through redox recycling of copper ions. Further, a dose-dependent inhibition of proliferation of breast cancer cells MDA-MB-231 by MN was found leading to pro-oxidant cell death, as assessed by MTT assay. Since levels of copper are considerably elevated in tissue, cell and serum during various malignancies, suggesting that cancer cells would be more subject to copper induced oxidative DNA breakage. Such a copper dependent pro-oxidant cytotoxic mechanism better explains the anticancer activity and preferential cytotoxicity of dietary phytochemicals against cancer cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Controllably annealed CuO-nanoparticle modified ITO electrodes: Characterisation and electrochemical studies

NASA Astrophysics Data System (ADS)

Wang, Tong; Su, Wen; Fu, Yingyi; Hu, Jingbo

2016-12-01

In this paper, we report a facile and controllable two-step approach to produce indium tin oxide electrodes modified by copper(II) oxide nanoparticles (CuO/ITO) through ion implantation and annealing methods. After annealing treatment, the surface morphology of the CuO/ITO substrate changed remarkably and exhibited highly electroactive sites and a high specific surface area. The effects of annealing treatment on the synthesis of CuO/ITO were discussed based on various instruments' characterisations, and the possible mechanism by which CuO nanoparticles were generated was also proposed in this work. Cyclic voltammetric results indicated that CuO/ITO electrodes exhibited effective catalytic responses toward glucose in alkaline solution. Under optimal experimental conditions, the proposed CuO/ITO electrode showed sensitivity of 450.2 μA cm-2 mM-1 with a linear range of up to ∼4.4 mM and a detection limit of 0.7 μM (S/N = 3). Moreover, CuO/ITO exhibited good poison resistance, reproducibility, and stability properties.

Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene

DOE PAGES

Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.; ...

2016-06-30

There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides aremore » surprisingly resistant to reduction and copper + species remain on the surface during the reaction. Furthermore, our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper + is key for lowering the onset potential and enhancing ethylene selectivity.« less

The impact of aging wine in high and low oxygen conditions on the fractionation of Cu and Fe in Chardonnay wine.

PubMed

Kontoudakis, Nikolaos; Guo, Anque; Scollary, Geoffrey R; Clark, Andrew C

2017-08-15

Solid-phase extraction has previously been used to fractionate copper and iron into hydrophobic, cationic and residual forms. This study showed the change in fractionated copper and iron in Chardonnay wines with 1-year of bottle aging under variable oxygen and protein concentrations. Wines containing protein in low oxygen conditions induced a decrease (20-50%) in total copper and increased the proportion of the hydrophobic copper fraction, associated with copper(I) sulfide. In contrast, protein stabilised wines showed a lower proportion of the hydrophobic copper fraction after 1-year of aging. In oxidative storage conditions, the total iron decreased by 60% when at high concentration, and the concentration of the residual fraction of both copper and iron increased. The results show that oxidative storage increases the most oxidative catalytic form of the metal, whilst changes during reductive storage depend on the extent of protein stabilisation of the wine. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

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

Hu, Zhuqin; Yu, Fengxiang; Gong, Ping

2014-04-15

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

Reduction of health care-associated infection indicators by copper oxide-impregnated textiles: Crossover, double-blind controlled study in chronic ventilator-dependent patients.

PubMed

Marcus, Esther-Lee; Yosef, Hana; Borkow, Gadi; Caine, Yehezkel; Sasson, Ady; Moses, Allon E

2017-04-01

Copper oxide has potent wide-spectrum biocidal properties. The purpose of this study is to determine if replacing hospital textiles with copper oxide-impregnated textiles reduces the following health care-associated infection (HAI) indicators: antibiotic treatment initiation events (ATIEs), fever days, and antibiotic usage in hospitalized chronic ventilator-dependent patients. A 7-month, crossover, double-blind controlled trial including all patients in 2 ventilator-dependent wards in a long-term care hospital. For 3 months (period 1), one ward received copper oxide-impregnated textiles and the other received untreated textiles. After a 1-month washout period of using regular textiles, for 3 months (period 2) the ward that received the treated textiles received the control textiles and vice versa. The personnel were blinded to which were treated or control textiles. There were no differences in infection control measures during the study. There were reductions of 29.3% (P = .002), 55.5% (P < .0001), 23.0% (P < .0001), and 27.5% (P < .0001) in the ATIEs, fever days (>37.6°C), days of antibiotic treatment, and antibiotic defined daily dose per 1,000 hospitalization days, respectively, when using the copper oxide-impregnated textiles. Use of copper oxide-impregnated biocidal textiles in a long-term care ward of ventilator-dependent patients was associated with a significant reduction of HAI indicators and antibiotic utilization. Using copper oxide-impregnated biocidal textiles may be an important measure aimed at reducing HAIs in long-term care medical settings. Copyright © 2017 Association for Professionals in Infection Control and Epidemiology, Inc. Published by Elsevier Inc. All rights reserved.

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

DOEpatents

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

1999-01-01

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

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

Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.

There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides aremore » surprisingly resistant to reduction and copper + species remain on the surface during the reaction. Furthermore, our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper + is key for lowering the onset potential and enhancing ethylene selectivity.« less

Effect of annealing temperature on the properties of copper oxide films prepared by dip coating technique

NASA Astrophysics Data System (ADS)

Raship, N. A.; Sahdan, M. Z.; Adriyanto, F.; Nurfazliana, M. F.; Bakri, A. S.

2017-01-01

Copper oxide films were grown on silicon substrates by sol-gel dip coating method. In order to study the effects of annealing temperature on the properties of copper oxide films, the temperature was varied from 200 °C to 450 °C. In the process of dip coating, the substrate is withdrawn from the precursor solution with uniform velocity to obtain a uniform coating before undergoing an annealing process to make the copper oxide film polycrystalline. The physical properties of the copper oxide films were measured by an X-ray diffraction (XRD), a field emission scanning electron microscope (FESEM), an atomic force microscopy (AFM) and a four point probe instrument. From the XRD results, we found that pure cuprite (Cu2O) phase can be obtained by annealing the films annealed at 200 °C. Films annealed at 300 °C had a combination phase which consists of tenorite (CuO) and cuprite (Cu2O) phase while pure tenorite (CuO) phase can be obtained at 450 °C annealing temperature. The surface microstructure showed that the grains size is increased whereas the surface roughness is increased and then decreases by increasing in annealing temperature. The films showed that the resistivity decreased with increasing annealing temperature. Consequently, it was observed that annealing temperature has strong effects on the structural, morphological and electrical properties of copper oxide films.

Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

PubMed

Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

2015-04-01

The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox Sorption of Oxygen Dissolved in Water on Copper Nanoparticles in an Ion Exchange Matrix

NASA Astrophysics Data System (ADS)

Vakhnin, D. D.; Pridorogina, V. E.; Polyanskii, L. N.; Kravchenko, T. A.; Gorshkov, V. S.

2018-01-01

The redox sorption of molecular oxygen from water by a thin granular layer of a copper-ion exchanger nanocomposite in the currentless mode and under cathodic polarization is studied. The speed of propagation of the boundaries of the chemical reaction of stepwise oxidation of copper nanoparticles under the conditions of polarization slows considerably. At the same time, the amount of electrochemically regenerated copper from the resulting oxides that is capable of interacting with oxygen again grows. The stationarity of the redox sorption of oxygen is due to the equality of the rates of oxidation and reduction of the metallic component of the composite.

Effects of dietary supplementation with vitamin C and vitamin E and their combination on growth performance, some biochemical parameters, and oxidative stress induced by copper toxicity in broilers.

PubMed

Cinar, Miyase; Yildirim, Ebru; Yigit, A Arzu; Yalcinkaya, Ilkay; Duru, Ozkan; Kisa, Uçler; Atmaca, Nurgul

2014-05-01

This study investigated effects of dietary supplementation with vitamin C, vitamin E on performance, biochemical parameters, and oxidative stress induced by copper toxicity in broilers. A total of 240, 1-day-old, broilers were assigned to eight groups with three replicates of 10 chicks each. The groups were fed on the following diets: control (basal diet), vitamin C (250 mg/kg diet), vitamin E (250 mg/kg diet), vitamin C + vitamin E (250 mg/kg + 250 mg/kg diet), and copper (300 mg/kg diet) alone or in combination with the corresponding vitamins. At the 6th week, the body weights of broilers were decreased in copper, copper + vitamin E, and copper + vitamin C + vitamin E groups compared to control. The feed conversion ratio was poor in copper group. Plasma aspartate aminotransferase, alanine aminotransferase, alkaline phosphatase activities, iron, copper concentrations, and erythrocyte malondialdehyde were increased; plasma vitamin A and C concentrations and erythrocyte superoxide dismutase were decreased in copper group compared to control. Glutathione peroxidase, vitamin C, and iron levels were increased; aspartate aminotransferase, alanine aminotransferase, alkaline phosphatase, and copper levels were decreased in copper + vitamin C group, while superoxide dismutase, glutathione peroxidase, and vitamin E concentrations were increased; aspartate aminotransferase, alanine aminotransferase, and alkaline phosphatase were decreased in copper with vitamin E group compared to copper group. The vitamin C concentrations were increased; copper, uric acid, aspartate aminotransferase, alanine aminotransferase, alkaline phosphatase, and malondialdehyde were decreased in copper + vitamin C + vitamin E group compared to copper group. To conclude, copper caused oxidative stress in broilers. The combination of vitamin C and vitamin E addition might alleviate the harmful effects of copper as demonstrated by decreased lipid peroxidation and hepatic enzymes.

Crystallization Behavior of Copper Smelter Slag During Molten Oxidation

NASA Astrophysics Data System (ADS)

Fan, Yong; Shibata, Etsuro; Iizuka, Atsushi; Nakamura, Takashi

2015-10-01

Copper slag is composed of iron silicate obtained by smelting copper concentrate and silica flux. One of the most important criteria for the utilization of this secondary resource is the recovery of iron from the slag matrix to decrease the volume of dumped slag. The molten oxidation process with crushing magnetic separation appears to be a more sustainable approach and is based on directly blowing oxidizing gas onto molten slag after the copper smelting process. In the current study, using an infrared furnace, the crystallization behavior of the slag during molten oxidation was studied to better understand the trade-off between magnetite and hematite precipitations, as assessed by X-ray diffraction (using an internal standard). Furthermore, the crystal morphology was examined using a laser microscope and Raman imaging system to understand the iron oxide transformation, and the distribution of impurities such as Cu, Zn, As, Cr, and Pb were complemented with scanning electron microscopy and energy dispersive spectroscopy. In addition, the reaction mechanism was investigated with a focus on the oxidation processes.

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

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

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

Copper-free route to triazole-modified peptidomimetic by the combination of two multicomponent reactions in one pot.

PubMed

Niu, Teng-fei; Gu, Lin; Yi, Wen-bin; Cai, Chun

2012-05-14

An efficient copper-free protocol for the synthesis of 5-methyl-1H-1,2,3-triazole-modified peptidomimetics through the combination of Ugi four-component reaction with a three-component cycloaddition, has been developed. The copper-free straightforward process is suitable for drug discovery. The chemoselective preparation of 1,4-disubstituted, triazole-modified peptidomimetics by using alkynyl substituted amines may have potential biological and synthetic application. At last, a "Lapinski type" analysis of the physical properties was performed, which is expected to help drug discovery.

Surface modification of Cu metal particles by the chemical reaction between the surface oxide layer and a halogen surfactant

NASA Astrophysics Data System (ADS)

Yokoyama, Shun; Takahashi, Hideyuki; Itoh, Takashi; Motomiya, Kenichi; Tohji, Kazuyuki

2014-01-01

Surface oxides on small (2-5 μm) copper metal particles can be removed by chemical reaction with tris(2,3-dibromopropyl) isocyanurate (TIC) in diethylene glycol mono-n-hexyl ether (DGHE) solution under mild conditions where metal particles are not damaged. Surface oxides convert to copper bromide species and subsequently dissolve into the solvent. It was found that resultant surface species are resistant to re-oxidation due to remaining surface bromides. This finding opens up a possibility to create microclines based on cheap copper nanoparticles.

Copper-catalyzed oxidative dimerizations of 3-N-hydroxy-aminoprop-1-enes to form 1,4-dihydroxy-2,3-diaminocyclohexanes with C2  symmetry.

PubMed

Ghorpade, Satish; Liu, Rai-Shung

2014-11-17

This work describes the one-step construction of complex and important molecular frameworks through copper-catalyzed oxidations of cheap tertiary amines. Copper-catalyzed aerobic oxidations of N-hydroxyaminopropenes to form C2 -symmetric N- and O-functionalized cyclohexanes are described. Such catalytic oxidations proceed with remarkable stereocontrol and high efficiency. Reductive cleavage of the two NO bonds of these products delivers 1,4-dihydroxy-2,3-diaminocyclohexanes, which are important skeletons of several bioactive molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced photoelectrocatalytic decomposition of copper cyanide complexes and simultaneous recovery of copper with a Bi2MoO6 electrode under visible light by EDTA/K4P2O7.

PubMed

Zhao, Xu; Zhang, Juanjuan; Qiao, Meng; Liu, Huijuan; Qu, Jiuhui

2015-04-07

Simultaneous photoelectrocatalytic (PEC) oxidation of cyanides and recovery of copper in a PEC reactor with a Bi(2)MoO(6) photoanode was investigated at alkaline conditions under visible light irradiation. The surface variation of the Bi(2)MoO(6) photoanode and titanium cathode was characterized. The Cu mass distribution onto the anode, in the solution, and onto the cathode was fully investigated. In the individual PEC oxidation of copper cyanides, the formation of a black copper oxide on the anode occurred. By keeping the initial cyanide concentration at 0.01 mM, the effect of EDTA/K(4)P(2)O(7) was examined at different molar ratios of EDTA/K(4)P(2)O(7) to cyanide. It was indicated that the oxidation of cyanides increased and simultaneous copper electrodeposition with zero value onto the cathode was feasible at pH 11. Under the optimal conditions, the total cyanide concentration was lowered from 250 to 5.0 mg/L, and the Cu recovery efficiency deposited onto the cathode was higher than 90%. Cyanate was the only product. The role of the photogenerated hole in the oxidation of cyanide ions was confirmed.

Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

PubMed

Zadlo, Andrzej; Pilat, Anna; Sarna, Michal; Pawlak, Anna; Sarna, Tadeusz

2017-12-01

With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

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

PubMed

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

2015-04-10

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

USE OF COMBUSTION SYNTHESIS IN PREPARING CERAMIC-MATRIX AND METAL-MATRIX COMPOSITE POWDERS

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

Weil, K. Scott; Hardy, John S.

A standard combustion-based approach typically used to synthesize nanosize oxide powders has been modified to prepare composite oxide-metal powders for subsequent densification via sintering or hot-pressing into ceramic- or metal-matrix composites. Copper and cerium nitrate salts were dissolved in the appropriate ratio in water and combined with glycine, then heated to cause autoignition. The ratio of glycine-to-total nitrate concentration was found to have the largest effect on the composition, agglomerate size, crystallite size, and dispersivity of phases in the powder product. After consolidation and sintering under reducing conditions, the resulting composite compact consists of a well-dispersed mixture of sub-micron sizemore » reinforcement particles in a fine-grained matrix.« less

UV-Vis-Induced Degradation of Phenol over Magnetic Photocatalysts Modified with Pt, Pd, Cu and Au Nanoparticles

PubMed Central

Wysocka, Izabela; Trzciński, Konrad; Łapiński, Marcin; Nowaczyk, Grzegorz; Zielińska-Jurek, Anna

2018-01-01

The combination of TiO2 photocatalyst and magnetic oxide nanoparticles enhances the separation and recoverable properties of nanosized TiO2 photocatalyst. Metal-modified (Me = Pd, Au, Pt, Cu) TiO2/SiO2@Fe3O4 nanocomposites were prepared by an ultrasonic-assisted sol-gel method. All prepared samples were characterized by X-ray powder diffraction (XRD) analysis, Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), Mott-Schottky analysis and photoluminescence spectroscopy (PL). Phenol oxidation pathways of magnetic photocatalysts modified with Pt, Pd, Cu and Au nanoparticles proceeded by generation of reactive oxygen species, which oxidized phenol to benzoquinone, hydroquinone and catechol. Benzoquinone and maleic acid were products, which were determined in the hydroquinone oxidation pathway. The highest mineralization rate was observed for Pd-TiO2/SiO2@Fe3O4 and Cu-TiO2/SiO2@Fe3O4 photocatalysts, which produced the highest concentration of catechol during photocatalytic reaction. For Pt-TiO2/SiO2@Fe3O4 nanocomposite, a lack of catechol after 60 min of irradiation resulted in low mineralization rate (CO2 formation). It is proposed that the enhanced photocatalytic activity of palladium and copper-modified photocatalysts is related to an increase in the amount of adsorption sites and efficient charge carrier separation, whereas the keto-enol tautomeric equilibrium retards the rate of phenol photomineralization on Au-TiO2/SiO2@Fe3O4. The magnetization hysteresis loop indicated that the obtained hybrid photocatalyst showed magnetic properties and therefore could be easily separated after treatment process. PMID:29316667

Free and esterified oxysterol: formation during copper-oxidation of low density lipoprotein and uptake by macrophages.

PubMed

Brown, A J; Dean, R T; Jessup, W

1996-02-01

We have defined the lipid composition of copper-oxidized LDL (Cu-oxLDL) and a macrophage-foam cell model generated by the uptake of this modified lipoprotein. An HPLC method previously developed by our group for the measurement of lipid oxidation products of LDL was extended to permit the analysis of an array of 7-ketocholesteryl esters. Gas chromatography was used for the quantitation of oxysterols (free and esterified) in Cu-oxLDL and their subsequent uptake by macrophages. LDL (1.0 mg protein/ml) was oxidized using Cu(II) (20 microM) for up to 48 h at 37 degrees C. Resident mouse peritoneal macrophages were incubated with 24 h Cu-oxLDL (50 micrograms/ml) for 24 h. In 24 h Cu-oxLDL, cholesterol comprised approximately 50% of total sterols, 7-ketocholesterol comprised approximately 30% with five other oxysterols comprising the remainder (7 alpha- and 7 beta-hydroxycholesterol, cholesterol alpha- and beta-epoxides, and 6 beta-hydroxycholesterol). Macrophages that were incubated with 24 h Cu-oxLDL displayed a profile of oxysterols remarkably similar to that of 24 h Cu-oxLDL itself. The majority of cholesteryl esters and 7-ketocholesteryl esters in Cu-oxLDL and in Cu-oxLDL-loaded macrophages contained fatty acyl chains which are presumed oxidized. This work represents a comprehensive survey of free and esterified oxysterols in Cu-oxLDL and Cu-oxLDL-loaded macrophages and provides a basis for exploring how oxysterols are metabolized by macrophages and authentic human foam cells, and how, in turn, these oxysterols influence cellular metabolism.

Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

PubMed

Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

2018-04-06

Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Examining mechanism of toxicity of copper oxide nanoparticles to Saccharomyces cerevisiae and Caenorhabditis elegans

NASA Astrophysics Data System (ADS)

Mashock, Michael J.

Copper oxide nanoparticles (CuO NPs) are an up and coming technology increasingly being used in industrial and consumer applications and thus may pose risk to humans and the environment. In the present study, the toxic effects of CuO NPs were studied with two model organisms Saccharomyces cerevisiae and Caenorhabditis elegans. The role of released Cu ions during dissolution of CuO NPs in growth media were studied with freshly suspended, aged NPs, and the released Cu 2+ fraction. Exposures to the different Cu treatments showed significant inhibition of S. cerevisiae cellular metabolic activity. Inhibition from the NPs was inversely proportional to size and was not fully explained by the released Cu ions. S. cerevisiae cultures grown under respiring conditions demonstrated greater metabolic sensitivity when exposed to CuO NPs compared to cultures undergoing fermentation. The cellular response to both CuO NPs and released Cu ions on gene expression was analyzed via microarray analysis after an acute exposure. It was observed that both copper exposures resulted in an increase in carbohydrate storage, a decrease in protein production, protein misfolding, increased membrane permeability, and cell cycle arrest. Cells exposed to NPs up-regulated genes related to oxidative phosphorylation but also may be inducing cell cycle arrest by a different mechanism than that observed with released Cu ions. The effect of CuO NPs on C. elegans was examined by using several toxicological endpoints. The CuO NPs displayed a more inhibitory effect, compared to copper sulfate, on nematode reproduction, feeding, and development. We investigated the effects of copper oxide nanoparticles and copper sulfate on neuronal health, a known tissue vulnerable to heavy metal toxicity. In transgenic C. eleganswith neurons expressing a green fluorescent protein reporter, neuronal degeneration was observed in up to 10% of the population after copper oxide nanoparticle exposure. Additionally, nematode mutant strains containing gene knockouts in the divalent-metal transporters smf-1 and smf-2 showed increased tolerance to copper exposure. These results lend credence to the hypothesis that some toxicological effects to eukaryotic organisms from copper oxide nanoparticle exposure may be due to properties specific to the nanoparticles and not solely from the released copper ions.

Copper-mediated DNA damage by the neurotransmitter dopamine and L-DOPA: A pro-oxidant mechanism.

PubMed

Rehmani, Nida; Zafar, Atif; Arif, Hussain; Hadi, Sheikh Mumtaz; Wani, Altaf A

2017-04-01

Oxidative DNA damage has been implicated in the pathogenesis of neurological disorders, cancer and ageing. Owing to the established link between labile copper concentrations and neurological diseases, it is critical to explore the interactions of neurotransmitters and drug supplements with copper. Herein, we investigate the pro-oxidant DNA damage induced by the interaction of L-DOPA and dopamine (DA) with copper. The DNA binding affinity order of the compounds has been determined by in silico molecular docking. Agarose gel electrophoresis reveals that L-DOPA and DA are able to induce strand scission in plasmid pcDNA3.1 (+/-) in a copper dependent reaction. These metabolites also cause cellular DNA breakage in human lymphocytes by mobilizing endogenous copper, as assessed by comet assay. Further, L-DOPA and DA-mediated DNA breaks were detected by the appearance of post-DNA damage sensitive marker γH2AX in cancer cell lines accumulating high copper. Immunofluorescence demonstrated the co-localization of downstream repair factor 53BP1 at the damaged induced γH2AX foci in cancer cells. The present study corroborates and provides a mechanism to the hypothesis that suggests metal-mediated oxidation of catecholamines contributes to the pathogenesis of neurodegenerative diseases. Copyright © 2017 Elsevier Ltd. All rights reserved.

Plant polyphenols mobilize nuclear copper in human peripheral lymphocytes leading to oxidatively generated DNA breakage: implications for an anticancer mechanism.

PubMed

Shamim, Uzma; Hanif, Sarmad; Ullah, M F; Azmi, Asfar S; Bhat, Showket H; Hadi, S M

2008-08-01

It was earlier proposed that an important anti-cancer mechanism of plant polyphenols may involve mobilization of endogenous copper ions, possibly chromatin-bound copper and the consequent pro-oxidant action. This paper shows that plant polyphenols are able to mobilize nuclear copper in human lymphocytes, leading to degradation of cellular DNA. A cellular system of lymphocytes isolated from human peripheral blood and comet assay was used for this purpose. Incubation of lymphocytes with neocuproine (a cell membrane permeable copper chelator) inhibited DNA degradation in intact lymphocytes. Bathocuproine, which is unable to permeate through the cell membrane, did not cause such inhibition. This study has further shown that polyphenols are able to degrade DNA in cell nuclei and that such DNA degradation is inhibited by neocuproine as well as bathocuproine (both of which are able to permeate the nuclear pore complex), suggesting that nuclear copper is mobilized in this reaction. Pre-incubation of lymphocyte nuclei with polyphenols indicates that it is capable of traversing the nuclear membrane. This study has also shown that polyphenols generate oxidative stress in lymphocyte nuclei which is inhibited by scavengers of reactive oxygen species (ROS) and neocuproine. These results indicate that the generation of ROS occurs through mobilization of nuclear copper resulting in oxidatively generated DNA breakage.

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

PubMed Central

Ibrahim, I; Lim, H. N; Huang, N. M; Pandikumar, A

2016-01-01

A photoelectrochemical (PEC) sensor with excellent sensitivity and detection toward copper (II) ions (Cu2+) was developed using a cadmium sulphide-reduced graphene oxide (CdS-rGO) nanocomposite on an indium tin oxide (ITO) surface, with triethanolamine (TEA) used as the sacrificial electron donor. The CdS nanoparticles were initially synthesized via the aerosol-assisted chemical vapor deposition (AACVD) method using cadmium acetate and thiourea as the precursors to Cd2+ and S2-, respectively. Graphene oxide (GO) was then dip-coated onto the CdS electrode and sintered under an argon gas flow (50 mL/min) for the reduction process. The nanostructured CdS was adhered securely to the ITO by a continuous network of rGO that also acted as an avenue to intensify the transfer of electrons from the conduction band of CdS. The photoelectrochemical results indicated that the ITO/CdS-rGO photoelectrode could facilitate broad UV-visible light absorption, which would lead to a higher and steady-state photocurrent response in the presence of TEA in 0.1 M KCl. The photocurrent decreased with an increase in the concentration of Cu2+ ions. The photoelectrode response for Cu2+ ion detection had a linear range of 0.5–120 μM, with a limit of detection (LoD) of 16 nM. The proposed PEC sensor displayed ultra-sensitivity and good selectivity toward Cu2+ ion detection. PMID:27176635

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

Induction of oxidative DNA damage by mesalamine in the presence of copper: a potential mechanism for mesalamine anticancer activity.

PubMed

Zimmerman, Ryan P; Jia, Zhenquan; Zhu, Hong; Vandjelovic, Nathan; Misra, Hara P; Wang, Jianmin; Li, Yunbo

2011-02-27

Mesalamine is the first line pharmacologic intervention for patients with ulcerative colitis, and recent epidemiologic studies have demonstrated a protective association between therapeutic use of the drug and colorectal carcinoma. However, the mechanism by which this protection is afforded has yet to be elucidated. Because copper is found at higher than normal concentrations in neoplastic cell nuclei and is known to interact with phenolic compounds to generate reactive oxygen species, we investigated whether the reaction of mesalamine/copper was able to induce oxidative DNA strand breaks in φX-174 RF I plasmid DNA, and the various components of the mechanism by which the reaction occurred. Plasmid DNA strand breaks were induced by pharmacologically relevant concentrations of mesalamine in the presence of a micromolar concentration of Cu(II), and damage was inhibited by bathocuproinedisulfonic acid (BCS) and catalase. Further, we showed that the reaction of copper with mesalamine consumed molecular oxygen, which was inhibited by BCS. Electron paramagnetic resonance spectral analysis of the reaction of copper/mesalamine indicated the presence of the hydroxyl radical, which was inhibited by both BCS and catalase. This study demonstrates for the first time that through a copper-redox cycling mechanism, the copper-mediated oxidation of mesalamine is a pro-oxidant interaction that generates hydroxyl radicals which may participate in oxidative DNA damage. These results demonstrate a potential mechanism of the anticancer effects of mesalamine in patients with ulcerative colitis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-02-16

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

Bioactive and biocompatible copper containing glass-ceramics with remarkable antibacterial properties and high cell viability designed for future in vivo trials.

PubMed

Popescu, R A; Magyari, K; Vulpoi, A; Trandafir, D L; Licarete, E; Todea, M; Ştefan, R; Voica, C; Vodnar, D C; Simon, S; Papuc, I; Baia, L

2016-07-19

In the present study our interest is focused on finding the efficiency of 60SiO2·(32 - x)CaO·8P2O5·xCuO (mol%) glass-ceramics, with 0 ≤ x ≤ 4 mol%, in terms of bioactivity, biocompatibility, antibacterial properties and cell viability in order to determine the most appropriate composition for their further use in in vivo trials. The sol-gel synthesized samples show a preponderantly amorphous structure with a few crystallization centers associated with the formation of an apatite and calcium carbonate crystalline phases. The Fourier Transform Infrared (FT-IR) spectra revealed slightly modified absorption bands due to the addition of copper oxide, while the information derived from the measurements performed by transmission electron microscopy, UV-vis and electron paramagnetic resonance spectroscopy showed the presence of ions and metallic copper species. X-Ray photoelectron spectroscopic analysis indicated the presence of copper metallic species, in a reduced amount, only on the sample surface with the highest Cu content. Regarding in vitro assessment of bioactivity, the results obtained by X-ray diffraction, FT-IR spectroscopy and scanning electron microscopy, demonstrated the formation of a calcium phosphate layer on all investigated sample surfaces. The inhibitory effect of the investigated samples was more significant on the Pseudomonas aeruginosa than the Staphylococcus aureus strain, the sample with the lowest concentration of copper oxide (0.5 mol%) being also the most efficient in both bacterial cultures. This sample also exhibits a very good bactericidal activity, for the other samples it was necessary to use a higher quantity to inhibit and kill the bacterial species. The secondary structure of adsorbed albumin presents few minor changes, indicating the biocompatibility of the glass-ceramics. The cell viability assay shows a good proliferation rate on samples with 0.5 and 1.5 mol% CuO, although all glass-ceramic samples exhibited a good in vivo tolerance.

Identification of the prooxidant site of human ceruloplasmin: a model for oxidative damage by copper bound to protein surfaces

NASA Technical Reports Server (NTRS)

Mukhopadhyay, C. K.; Mazumder, B.; Lindley, P. F.; Fox, P. L.

1997-01-01

Free transition metal ions oxidize lipids and lipoproteins in vitro; however, recent evidence suggests that free metal ion-independent mechanisms are more likely in vivo. We have shown previously that human ceruloplasmin (Cp), a serum protein containing seven Cu atoms, induces low density lipoprotein oxidation in vitro and that the activity depends on the presence of a single, chelatable Cu atom. We here use biochemical and molecular approaches to determine the site responsible for Cp prooxidant activity. Experiments with the His-specific reagent diethylpyrocarbonate (DEPC) showed that one or more His residues was specifically required. Quantitative [14C]DEPC binding studies indicated the importance of a single His residue because only one was exposed upon removal of the prooxidant Cu. Plasmin digestion of [14C]DEPC-treated Cp (and N-terminal sequence analysis of the fragments) showed that the critical His was in a 17-kDa region containing four His residues in the second major sequence homology domain of Cp. A full length human Cp cDNA was modified by site-directed mutagenesis to give His-to-Ala substitutions at each of the four positions and was transfected into COS-7 cells, and low density lipoprotein oxidation was measured. The prooxidant site was localized to a region containing His426 because CpH426A almost completely lacked prooxidant activity whereas the other mutants expressed normal activity. These observations support the hypothesis that Cu bound at specific sites on protein surfaces can cause oxidative damage to macromolecules in their environment. Cp may serve as a model protein for understanding mechanisms of oxidant damage by copper-containing (or -binding) proteins such as Cu, Zn superoxide dismutase, and amyloid precursor protein.

Comparison between micro- and nanosized copper oxide and water soluble copper chloride: interrelationship between intracellular copper concentrations, oxidative stress and DNA damage response in human lung cells.

PubMed

Strauch, Bettina Maria; Niemand, Rebecca Katharina; Winkelbeiner, Nicola Lisa; Hartwig, Andrea

2017-08-01

Nano- and microscale copper oxide particles (CuO NP, CuO MP) are applied for manifold purposes, enhancing exposure and thus the potential risk of adverse health effects. Based on the pronounced in vitro cytotoxicity of CuO NP, systematic investigations on the mode of action are required. Therefore, the impact of CuO NP, CuO MP and CuCl 2 on the DNA damage response on transcriptional level was investigated by quantitative gene expression profiling via high-throughput RT-qPCR. Cytotoxicity, copper uptake and the impact on the oxidative stress response, cell cycle regulation and apoptosis were further analysed on the functional level. Cytotoxicity of CuO NP was more pronounced when compared to CuO MP and CuCl 2 in human bronchial epithelial BEAS-2B cells. Uptake studies revealed an intracellular copper overload in the soluble fractions of both cytoplasm and nucleus, reaching up to millimolar concentrations in case of CuO NP and considerably lower levels in case of CuO MP and CuCl 2 . Moreover, CuCl 2 caused copper accumulation in the nucleus only at cytotoxic concentrations. Gene expression analysis in BEAS-2B and A549 cells revealed a strong induction of uptake-related metallothionein genes, oxidative stress-sensitive and pro-inflammatory genes, anti-oxidative defense-associated genes as well as those coding for the cell cycle inhibitor p21 and the pro-apoptotic Noxa and DR5. While DNA damage inducible genes were activated, genes coding for distinct DNA repair factors were down-regulated. Modulation of gene expression was most pronounced in case of CuO NP as compared to CuO MP and CuCl 2 and more distinct in BEAS-2B cells. GSH depletion and activation of Nrf2 in HeLa S3 cells confirmed oxidative stress induction, mainly restricted to CuO NP. Also, cell cycle arrest and apoptosis induction were most distinct for CuO NP. The high cytotoxicity and marked impact on gene expression by CuO NP can be ascribed to the strong intracellular copper ion release, with subsequent copper accumulation in the cytoplasm and the nucleus. Modulation of gene expression by CuO NP appeared to be primarily oxidative stress-related and was more pronounced in redox-sensitive BEAS-2B cells. Regarding CuCl 2 , relevant modulations of gene expression were restricted to cytotoxic concentrations provoking impaired copper homoeostasis.

Copper Oxide Nanograss for Efficient and Stable Photoelectrochemical Hydrogen Production by Water Splitting

NASA Astrophysics Data System (ADS)

Borkar, Rajnikant; Dahake, Rashmi; Rayalu, Sadhana; Bansiwal, Amit

2018-03-01

A biphasic copper oxide thin film of grass-like appendage morphology is synthesized by two-step electro-deposition method and later investigated for photoelectrochemical (PEC) water splitting for hydrogen production. Further, the thin film was characterized by UV-Visible spectroscopy, x-ray diffraction (XRD), Scanning electron microscopy (SEM) and PEC techniques. The XRD analysis confirms formation of biphasic copper oxide phases, and SEM reveals high surface area grass appendage-like morphology. These grass appendage structures exhibit a high cathodic photocurrent of - 1.44 mAcm-2 at an applied bias of - 0.7 (versus Ag/AgCl) resulting in incident to photon current efficiency (IPCE) of ˜ 10% at 400 nm. The improved light harvesting and charge transport properties of grass appendage structured biphasic copper oxides makes it a potential candidate for PEC water splitting for hydrogen production.

Studies on electrochemical glucose sensing, antimicrobial activity and cytotoxicity of fabricated copper nanoparticle immobilized chitin nanostructure.

PubMed

Solairaj, Dhanasekaran; Rameshthangam, Palanivel; Muthukumaran, Palanisamy; Wilson, Jeyaraj

2017-08-01

In this study, copper nanoparticle immobilized chitin nanocomposite (CNP/CuNP) was synthesized and used for the development of non-enzymatic electrochemical sensor. The CNP/CuNP was characterized by X-ray diffraction (XRD), fourier transform infra red (FTIR) spectroscopy and high resolution transmission electron microscopy (HRTEM) analysis. The glucose sensing property of CNP/CuNP was investigated by cyclic voltammetry (CV) and chronoamperometry (CA). As a result of the synergistic effect of CNP and CuNP, the modified electrode displayed effective electro-oxidation of glucose in 0.1M NaOH solution. At 0.45V potential the modified electrode showed response towards glucose in the linear range of 1-1000μM with a lowest detection limit of 0.776μM with better selectivity and stability. In addition, the antimicrobial activity of CNP/CuNP was evaluated against bacterial and fungal strains. CNP/CuNP displayed enhanced antimicrobial activity when compared to CNP and CuNP alone. Similarly, cytotoxicity of CNP/CuNP was tested against Artemia salina, which showed no toxic effect in the tested concentration. Copyright © 2017 Elsevier B.V. All rights reserved.

Divalent Copper as a Major Triggering Agent in Alzheimer's Disease.

PubMed

Brewer, George J

2015-01-01

Alzheimer's disease (AD) is at epidemic proportions in developed countries, with a steady increase in the early 1900 s, and then exploding over the last 50 years. This epidemiology points to something causative in the environment of developed countries. This paper will review the considerable evidence that that something could be inorganic copper ingestion. The epidemic parallels closely the spread of copper plumbing, with copper leached from the plumbing into drinking water being a main causal feature, aided by the increasingly common use of supplement pills containing copper. Inorganic copper is divalent copper, or copper-2, while we now know that organic copper, or copper in foods, is primarily monovalent copper, or copper-1. The intestinal transport system, Ctr1, absorbs copper-1 and the copper moves to the liver, where it is put into safe channels. Copper-2 is not absorbed by Ctr1, and some of it bypasses the liver and goes directly into the blood, where it appears to be exquisitely toxic to brain cognition. Thus, while aggregation of amyloid-β has been postulated to be the cause of AD under current dogma, the great increase in prevalence over the last century appears to be due to ingestion of copper-2, which may be causing the aggregation, and/or increasing the oxidant toxicity of the aggregates. An alternative hypothesis proposes that oxidant stress is the primary injuring agent, and under this hypothesis, copper-2 accumulation in the brain may be a causal factor of the oxidant injury. Thus, irrespective of which hypothesis is correct, AD can be classified, at least in part, as a copper-2 toxicity disease. It is relatively easy to avoid copper-2 ingestion, as discussed in this review. If most people begin avoiding copper-2 ingestion, perhaps the epidemic of this serious disease can be aborted.

In vivo toxic effects of 4-methoxy-5-hydroxy-canthin-6-one in zebrafish embryos via copper dyshomeostasis and oxidative stress.

PubMed

Gong, Guiyi; Jiang, Lingling; Lin, Qinghua; Liu, Wenyuan; He, Ming-Fang; Zhang, Jie; Feng, Feng; Qu, Wei; Xie, Ning

2018-01-01

Dysfunction of copper homeostasis can lead to a host of disorders, which might be toxic sometimes. 4-Methoxy-5-hydroxy-canthin-6-one (CAN) is one of the major constituents from Picrasma quassioides and responsible for its therapeutic effects. In this work, we evaluated the toxic effect of CAN (7.5μM) on zebrafish embryos. CAN treatment decreased survival, delayed hatching time and induced malformations (loss of pigmentation, pericardial edema, as well as hematologic and neurologic abnormalities). Besides, exogenous copper supplementation rescued the pigmentation and cardiovascular defects in CAN-treated embryos. Further spectroscopic studies revealed a copper-chelating activity of CAN. Then its regulation on the expressions of copper homeostasis related genes also be analyzed. In addition, CAN lowered the total activity of SOD, elevated the ROS production and altered the oxidative related genes transcriptions, which led to oxidative stress. In conclusion, we demonstrated that CAN (7.5μM) might exert its toxic effects in zebrafish embryos by causing copper dyshomeostasis and oxidative stress. It will give insight into the risk assessment and prevention of CAN-mediated toxicity. Copyright © 2017 Elsevier Inc. All rights reserved.

Characterization and recovery of copper values from discarded slag.

PubMed

Das, Bisweswar; Mishra, Barada Kanta; Angadi, Shivakumar; Pradhan, Siddharth Kumar; Prakash, Sandur; Mohanty, Jayakrushna

2010-06-01

In any copper smelter large quantities of copper slag are discarded as waste material causing space and environmental problems. This discarded slag contains important amounts of metallic values such as copper and iron. The recovery of copper values from an Indian smelter slag that contains 1.53% Cu, 39.8% Fe and 34.65% SiO(2) was the focus of the present study. A complete investigation of the different phases present in the slag has been carried out by means of optical microscopy, Raman spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) techniques. It is observed that iron and silica are mostly associated with the fayalite phase whereas copper is present in both oxide and sulfide phases. These oxide and sulfide phases of copper are mostly present within the slag phase and to some extent the slag is also embedded inside the oxide and sulfide phases. The recovery of copper values from the discarded slag has been explored by applying a flotation technique using conventional sodium isopropyl xanthate (SIX) as the collector. The effects of flotation parameters such as pH and collector concentration are investigated. Under optimum flotation conditions, it is possible to achieve 21% Cu with more than 80% recovery.

High-performance flexible supercapacitors based on electrochemically tailored three-dimensional reduced graphene oxide networks.

PubMed

Purkait, Taniya; Singh, Guneet; Kumar, Dinesh; Singh, Mandeep; Dey, Ramendra Sundar

2018-01-12

A simple approach for growing porous electrochemically reduced graphene oxide (pErGO) networks on copper wire, modified with galvanostatically deposited copper foam is demonstrated. The as-prepared pErGO networks on the copper wire are directly used to fabricate solid-state supercapacitor. The pErGO-based supercapacitor can deliver a specific capacitance (C sp ) as high as 81±3 F g -1 at 0.5 A g -1 with polyvinyl alcohol/H 3 PO 4 gel electrolyte. The C sp per unit length and area are calculated as 40.5 mF cm -1 and 283.5 mF cm -2 , respectively. The shape of the voltammogram retained up to high scan rate of 100 V s -1 . The pErGO-based supercapacitor device exhibits noticeably high charge-discharge cycling stability, with 94.5% C sp retained even after 5000 cycles at 5 A g -1 . Nominal change in the specific capacitance, as well as the shape of the voltammogram, is observed at different bending angles of the device even after 5000 cycles. The highest energy density of 11.25 W h kg -1 and the highest power density of 5 kW kg -1 are also achieved with this device. The wire-based supercapacitor is scalable and highly flexible, which can be assembled with/without a flexible substrate in different geometries and bending angles for illustrating promising use in smart textile and wearable device.

Native oxide formation on pentagonal copper nanowires: A TEM study

NASA Astrophysics Data System (ADS)

Hajimammadov, Rashad; Mohl, Melinda; Kordas, Krisztian

2018-06-01

Hydrothermally synthesized copper nanowires were allowed to oxidize in air at room temperature and 30% constant humidity for the period of 22 days. The growth of native oxide layer was followed up by high-resolution transmission electron microscopy and diffraction to reveal and understand the kinetics of the oxidation process. Copper oxides appear in the form of differently oriented crystalline phases around the metallic core as a shell-like layer (Cu2O) and as nanoscopic islands (CuO) on the top of that. Time dependent oxide thickness data suggests that oxidation follows the field-assisted growth model at the beginning of the process, as practically immediately an oxide layer of ∼2.8 nm thickness develops on the surface. However, after this initial rapid growth, the local field attenuates and the classical parabolic diffusion limited growth plays the main role in the oxidation. Because of the single crystal facets on the side surface of penta-twinned Cu nanowires, the oxidation rate in the diffusion limited regime is lower than in polycrystalline films.

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

NASA Astrophysics Data System (ADS)

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

2003-09-01

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

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

NASA Technical Reports Server (NTRS)

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

1983-01-01

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

Controlled atmosphere for fabrication of cermet electrodes

DOEpatents

Ray, Siba P.; Woods, Robert W.

1998-01-01

A process for making an inert electrode composite wherein a metal oxide and a metal are reacted in a gaseous atmosphere at an elevated temperature of at least about 750.degree. C. The metal oxide is at least one of the nickel, iron, tin, zinc and zirconium oxides and the metal is copper, silver, a mixture of copper and silver or a copper-silver alloy. The gaseous atmosphere has an oxygen content that is controlled at about 5-3000 ppm in order to obtain a desired composition in the resulting composite.

Controlled atmosphere for fabrication of cermet electrodes

DOEpatents

Ray, S.P.; Woods, R.W.

1998-08-11

A process is disclosed for making an inert electrode composite wherein a metal oxide and a metal are reacted in a gaseous atmosphere at an elevated temperature of at least about 750 C. The metal oxide is at least one of the nickel, iron, tin, zinc and zirconium oxides and the metal is copper, silver, a mixture of copper and silver or a copper-silver alloy. The gaseous atmosphere has an oxygen content that is controlled at about 5--3000 ppm in order to obtain a desired composition in the resulting composite. 2 figs.

Electrothermal atomic absorption spectrometric determination of copper in nickel-base alloys with various chemical modifiers*1

NASA Astrophysics Data System (ADS)

Tsai, Suh-Jen Jane; Shiue, Chia-Chann; Chang, Shiow-Ing

1997-07-01

The analytical characteristics of copper in nickel-base alloys have been investigated with electrothermal atomic absorption spectrometry. Deuterium background correction was employed. The effects of various chemical modifiers on the analysis of copper were investigated. Organic modifiers which included 2-(5-bromo-2-pyridylazo)-5-(diethylamino-phenol) (Br-PADAP), ammonium citrate, 1-(2-pyridylazo)-naphthol, 4-(2-pyridylazo)resorcinol, ethylenediaminetetraacetic acid and Triton X-100 were studied. Inorganic modifiers palladium nitrate, magnesium nitrate, aluminum chloride, ammonium dihydrogen phosphate, hydrogen peroxide and potassium nitrate were also applied in this work. In addition, zirconium hydroxide and ammonium hydroxide precipitation methods have also been studied. Interference effects were effectively reduced with Br-PADAP modifier. Aqueous standards were used to construct the calibration curves. The detection limit was 1.9 pg. Standard reference materials of nickel-base alloys were used to evaluate the accuracy of the proposed method. The copper contents determined with the proposed method agreed closely with the certified values of the reference materials. The recoveries were within the range 90-100% with relative standard deviation of less than 10%. Good precision was obtained.

VAPOR PHASE MERCURY SORPTION BY ORGANIC SULFIDE MODIFIED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

EPA Science Inventory

Novel organic sulfide modified bimetallic iron-copper nanoparticle aggregate sorbent materials have been synthesized for removing elemental mercury from vapor streams at elevated temperatures (120-140 °C). Silane based (disulfide silane and tetrasulfide silane) and alkyl sulfide ...

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

PubMed Central

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

2011-01-01

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

Determination of total and electrolabile copper in agricultural soil by using disposable modified-carbon screen-printed electrodes.

PubMed

Faucher, Stéphane; Cugnet, Cyril; Authier, Laurent; Lespes, Gaëtane

2014-02-01

The objective of the study is to evaluate modified-carbon screen-printed working electrodes (SPE) combined with square wave anodic stripping voltammetry (SWASV) to determine electrolabile and total copper in soils with the perspective to assess the environmental hazard resulting from copper anthropogenic contamination. The voltammetric method was investigated using a mineralized certified reference soil such that it can be assumed that the copper was totally under electrolabile form in the solution of mineralized soil. In optimal conditions, a copper recovery of 97% and a relative standard deviation (RSD) of 9% were found. The limits of detection and quantification for copper were 0.4 and 1.3 μg L(-1), respectively. Finally, the method was applied on soil leachates, which allowed evaluating the cupric transfer from the soil to the leachates and quantifying the electrolabile copper part in leachates.

Sorbent for use in hot gas desulfurization

DOEpatents

Gasper-Galvin, Lee D.; Atimtay, Aysel T.

1993-01-01

A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.

Conserved active site residues limit inhibition of a copper-containing nitrite reductase by small molecules.

PubMed

Tocheva, Elitza I; Eltis, Lindsay D; Murphy, Michael E P

2008-04-15

The interaction of copper-containing dissimilatory nitrite reductase from Alcaligenes faecalis S-6 ( AfNiR) with each of five small molecules was studied using crystallography and steady-state kinetics. Structural studies revealed that each small molecule interacted with the oxidized catalytic type 2 copper of AfNiR. Three small molecules (formate, acetate and nitrate) mimic the substrate by having at least two oxygen atoms for bidentate coordination to the type 2 copper atom. These three anions bound to the copper ion in the same asymmetric, bidentate manner as nitrite. Consistent with their weak inhibition of the enzyme ( K i >50 mM), the Cu-O distances in these AfNiR-inhibitor complexes were approximately 0.15 A longer than that observed in the AfNiR-nitrite complex. The binding mode of each inhibitor is determined in part by steric interactions with the side chain of active site residue Ile257. Moreover, the side chain of Asp98, a conserved residue that hydrogen bonds to type 2 copper-bound nitrite and nitric oxide, was either disordered or pointed away from the inhibitors. Acetate and formate inhibited AfNiR in a mixed fashion, consistent with the occurrence of second acetate binding site in the AfNiR-acetate complex that occludes access to the type 2 copper. A fourth small molecule, nitrous oxide, bound to the oxidized metal in a side-on fashion reminiscent of nitric oxide to the reduced copper. Nevertheless, nitrous oxide bound at a farther distance from the metal. The fifth small molecule, azide, inhibited the reduction of nitrite by AfNiR most strongly ( K ic = 2.0 +/- 0.1 mM). This ligand bound to the type 2 copper center end-on with a Cu-N c distance of approximately 2 A, and was the only inhibitor to form a hydrogen bond with Asp98. Overall, the data substantiate the roles of Asp98 and Ile257 in discriminating substrate from other small anions.

Effect of сopper сoating on fibers made of aluminum alloy, titanium, and FeCrAl alloy on surface morphology and activity in CO oxidation

NASA Astrophysics Data System (ADS)

Lukiyanchuk, I. V.; Rudnev, V. S.; Serov, M. M.; Krit, B. L.; Lukiyanchuk, G. D.; Nedozorov, P. M.

2018-04-01

The catalytic activity of both copper fibers and copper-coated fibers of a diameter of 50-100 μm made of aluminum alloy, technical grade titanium, and FeCrAl alloy in CO oxidation has been estimated. Metal fibers have been fabricated by the method of pendant drop melt extraction (PDME). The fibers copper plating was carried out by chemical and electrochemical methods. The composition and structure of samples and coatings before and after catalytic tests have been characterized by the methods of scanning electron microscopy, energy-dispersive analysis, and X-ray fluorescence analysis. It has been shown that the catalytic activity of copper-coated fibers made of FeCrAl alloy in the reaction of CO oxidation is not inferior to that of copper fibers.

Role of alloying elements in adhesive transfer and friction of copper-base alloys

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1978-01-01

Sliding friction experiments were conducted in a vacuum with binary-copper alloy riders sliding against a conventional bearing-steel surface with normal residual oxides present. The binary alloys contained 1 atomic percent of various alloying elements. Auger spectroscopy analysis was used to monitor the adhesive transfer of the copper alloys to the bearing-steel surface. A relation was found to exist between adhesive transfer and the reaction potential and free energy of formation of the alloying element in the copper. The more chemically active the element and the more stable its oxide, the greater was the adhesive transfer and wear of the copper alloy. Transfer occurred in all the alloys except copper-gold after relatively few (25) passes across the steel surface.

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

PubMed

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

2009-11-01

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

Some metal-graphite and metal-ceramic composites for use as high energy brake lining materials

NASA Technical Reports Server (NTRS)

Bill, R. C.

1974-01-01

Materials were studied as candidates for development as potential new aircraft brake lining materials. These families were (1) copper-graphite composites; (2) nickel-graphite composites; (3) copper - rare-earth-oxide (gadolinium oxide (Gd2O3) or lanthanum oxide (La2O3)) composites and copper - rare-earth-oxide (La2O3) - rare-earth-fluoride (lanthanum fluoride (LaF3)) composites; (4) nickel - rare-earth-oxide composites and nickel - rare-earth-oxide - rare-earth-fluoride composites. For comparison purposes, a currently used metal-ceramic composite was also studied. Results showed that the nickel-Gd2O3 and nickel-La2O3-LaF3 composites were comparable or superior in friction and wear performance to the currently used composite and therefore deserve to be considered for further development.

Understanding the antimicrobial activity behind thin- and thick-rolled copper plates.

PubMed

Yousuf, Basit; Ahire, Jayesh J; Dicks, Leon M T

2016-06-01

The aim of this study was to compare the antibacterial properties of the surfaces of copper plates that were rolled to a thickness of 25 and 100 μm. Differences in topology of 25- and 100-μm-thick copper plates were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD). Antibacterial activity of the copper surfaces was tested against strains of Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Listeria monocytogenes, Salmonella typhimurium, Streptococcus sp. BY1, Enterococcus sp. BY2, and Bacillus cereus BY3. Changes in viable cell numbers were determined by plating onto optimal growth media and staining with LIVE/DEAD BacLight™. Changes in metabolic activity were recorded by expression of the luciferase (lux) gene. Cell morphology was studied using SEM. Accumulation and diffusion of copper from cells were recorded using inductively coupled plasma mass spectroscopy (ICP-MS). Lipid and protein oxidation were recorded spectrophotometrically. Surfaces of 25-μm-thick copper plates were rough compared to that of 100-μm-thick copper plates. For most species, a five-log reduction in cell numbers, cell membrane instability, and a decline in metabolic activity were recorded after 15 min of exposure to 25-μm-thick copper plates. Copper accumulated in the cells, and lipids and proteins were oxidized. The rough surface of thinner copper plates (25 μm thick) released more copper and was more antimicrobial compared to thicker (100 μm) copper plates. Cell death was attributed to destabilization of the cell membrane, lipid peroxidation, and protein oxidation.

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

PubMed

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

2004-12-21

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

Effect of native oxide layers on copper thin-film tensile properties: A reactive molecular dynamics study

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

Skarlinski, Michael D., E-mail: michael.skarlinski@rochester.edu; Quesnel, David J.; Department of Mechanical Engineering, University of Rochester, Rochester, New York 14627

2015-12-21

Metal-oxide layers are likely to be present on metallic nano-structures due to either environmental exposure during use, or high temperature processing techniques such as annealing. It is well known that nano-structured metals have vastly different mechanical properties from bulk metals; however, difficulties in modeling the transition between metallic and ionic bonding have prevented the computational investigation of the effects of oxide surface layers. Newly developed charge-optimized many body [Liang et al., Mater. Sci. Eng., R 74, 255 (2013)] potentials are used to perform fully reactive molecular dynamics simulations which elucidate the effects that metal-oxide layers have on the mechanical propertiesmore » of a copper thin-film. Simulated tensile tests are performed on thin-films while using different strain-rates, temperatures, and oxide thicknesses to evaluate changes in yield stress, modulus, and failure mechanisms. Findings indicate that copper-thin film mechanical properties are strongly affected by native oxide layers. The formed oxide layers have an amorphous structure with lower Cu-O bond-densities than bulk CuO, and a mixture of Cu{sub 2}O and CuO charge character. It is found that oxidation will cause modifications to the strain response of the elastic modulii, producing a stiffened modulii at low temperatures (<75 K) and low strain values (<5%), and a softened modulii at higher temperatures. While under strain, structural reorganization within the oxide layers facilitates brittle yielding through nucleation of defects across the oxide/metal interface. The oxide-free copper thin-film yielding mechanism is found to be a tensile-axis reorientation and grain creation. The oxide layers change the observed yielding mechanism, allowing for the inner copper thin-film to sustain an FCC-to-BCC transition during yielding. The mechanical properties are fit to a thermodynamic model based on classical nucleation theory. The fit implies that the oxidation of the films reduces the activation volume for yielding.« less

Bioavailable copper modulates oxidative phosphorylation and growth of tumors

PubMed Central

Ishida, Seiko; Andreux, Pénélope; Poitry-Yamate, Carole; Auwerx, Johan; Hanahan, Douglas

2013-01-01

Copper is an essential trace element, the imbalances of which are associated with various pathological conditions, including cancer, albeit via largely undefined molecular and cellular mechanisms. Here we provide evidence that levels of bioavailable copper modulate tumor growth. Chronic exposure to elevated levels of copper in drinking water, corresponding to the maximum allowed in public water supplies, stimulated proliferation of cancer cells and de novo pancreatic tumor growth in mice. Conversely, reducing systemic copper levels with a chelating drug, clinically used to treat copper disorders, impaired both. Under such copper limitation, tumors displayed decreased activity of the copper-binding mitochondrial enzyme cytochrome c oxidase and reduced ATP levels, despite enhanced glycolysis, which was not accompanied by increased invasiveness of tumors. The antiproliferative effect of copper chelation was enhanced when combined with inhibitors of glycolysis. Interestingly, larger tumors contained less copper than smaller tumors and exhibited comparatively lower activity of cytochrome c oxidase and increased glucose uptake. These results establish copper as a tumor promoter and reveal that varying levels of copper serves to regulate oxidative phosphorylation in rapidly proliferating cancer cells inside solid tumors. Thus, activation of glycolysis in tumors may in part reflect insufficient copper bioavailability in the tumor microenvironment. PMID:24218578

High-temperature sorbent method for removal of sulfur-containing gases from gaseous mixtures

DOEpatents

Young, J.E.; Jalan, V.M.

1982-07-07

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorbtion capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

High-temperature sorbent method for removal of sulfur containing gases from gaseous mixtures

DOEpatents

Young, J.E.; Jalan, V.M.

1984-06-19

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorption capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

High-temperature sorbent method for removal of sulfur containing gases from gaseous mixtures

DOEpatents

Young, John E.; Jalan, Vinod M.

1984-01-01

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorption capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

[Biohydrometallurgical technology of a complex copper concentrate process].

PubMed

Murav'ev, M I; Fomchenko, N V; Kondrat'eva, T F

2011-01-01

Leaching of sulfide-oxidized copper concentrate of the Udokan deposit ore with a copper content of 37.4% was studied. In the course of treatment in a sulfuric acid solution with pH 1.2, a copper leaching rate was 6.9 g/kg h for 22 h, which allowed extraction of 40.6% of copper. As a result of subsequent chemical leaching at 80 degrees C during 7 h with a solution of sulphate ferric iron obtained after bio-oxidation by an association of microorganisms, the rate of copper recovery was 52.7 g/kg h. The total copper recovery was 94.5% (over 29 h). Regeneration of the Fe3+ ions was carried out by an association of moderately thermophilic microorganisms, including bacteria of genus Sulfobacillus and archaea of genus Ferroplasma acidiphilum, at 1.0 g/l h at 40 degrees C in the presence of 3% solids obtained by chemical leaching of copper concentrate. A technological scheme of a complex copper concentrate process with the use of bacterial-chemical leaching is proposed.

Activation of the MAPK11/12/13/14 (p38 MAPK) pathway regulates the transcription of autophagy genes in response to oxidative stress induced by a novel copper complex in HeLa cells.

PubMed

Zhong, Wu; Zhu, Haichuan; Sheng, Fugeng; Tian, Yonglu; Zhou, Jun; Chen, Yingyu; Li, Song; Lin, Jian

2014-07-01

Transition metal copper (Cu) can exist in oxidized or reduced states in cells, leading to cytotoxicity in cancer cells through oxidative stress. Recently, copper complexes are emerging as a new class of anticancer compounds. Here, we report that a novel anticancer copper complex (HYF127c/Cu) induces oxidative stress-dependent cell death in cancer cells. Further, transcriptional analysis revealed that oxidative stress elicits broad transcriptional changes of genes, in which autophagy-related genes are significantly changed in HYF127c/Cu-treated cells. Consistently, autophagy was induced in HYF127c/Cu-treated cells and inhibitors of autophagy promoted cell death induced by HYF127c/Cu. Further analysis identified that the MAPK11/12/13/14 (formerly known as p38 MAPK) pathway was also activated in HYF127c/Cu-treated cells. Meanwhile, the MAPK11/12/13/14 inhibitor SB203580 downregulated autophagy by inhibiting the transcription of the autophagy genes MAP1LC3B, BAG3, and HSPA1A, and promoted HYF127c/Cu-induced cell death. These data suggest that copper-induced oxidative stress will induce protective autophagy through transcriptional regulation of autophagy genes by activation of the MAPK11/12/13/14 pathway in HeLa cells.

Growth and characterization of single phase Cu{sub 2}O by thermal oxidation of thin copper films

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

Choudhary, Sumita; Sarma, J. V. N.; Gangopadhyay, Subhashis, E-mail: subhagan@yahoo.com

2016-04-13

We report a simple and efficient technique to form high quality single phase cuprous oxide films on glass substrate using thermal evaporation of thin copper films followed by controlled thermal oxidation in air ambient. Crystallographic analysis and oxide phase determination, as well as grain size distribution have been studied using X-ray diffraction (XRD) method, while scanning electron microscopy (SEM) has been utilized to investigate the surface morphology of the as grown oxide films. The formation of various copper oxide phases is found to be highly sensitive to the oxidation temperature and a crystalline, single phase cuprous oxide film can bemore » achieved for oxidation temperatures between 250°C to 320°C. Cu{sub 2}O film surface appeared in a faceted morphology in SEM imaging and a direct band gap of about 2.1 eV has been observed in UV-visible spectroscopy. X-ray photoelectron spectroscopy (XPS) confirmed a single oxide phase formation. Finally, a growth mechanism of the oxide film has also been discussed.« less

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

PubMed

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

2013-02-01

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

Copper increases the ability of 6-hydroxydopamine to generate oxidative stress and the ability of ascorbate and glutathione to potentiate this effect: potential implications in Parkinson's disease.

PubMed

Cruces-Sande, Antón; Méndez-Álvarez, Estefanía; Soto-Otero, Ramón

2017-06-01

Copper is an essential metal for the function of many proteins related to important cellular reactions and also involved in the synaptic transmission. Although there are several mechanisms involved in copper homeostasis, a dysregulation in this process can result in serious neurological consequences, including degeneration of dopaminergic neurons. 6-Hydroxydopamine is a dopaminergic neurotoxin mainly used in experimental models of Parkinson's disease, whose neurotoxicity has been related to its ability to generate free radicals. In this study, we examined the effects induced by copper on 6-OHDA autoxidation. Our data show that both Cu + and Cu 2+ caused an increase in • OH production by 6-OHDA autoxidation, which was accompanied by an increase in the rate of both p-quinone formation and H 2 O 2 accumulation. The presence of ascorbate greatly enhanced this process by establishing a redox cycle which regenerates 6-OHDA from its p-quinone. However, the presence of glutathione did not change significantly the copper-induced effects. We observed that copper is able to potentiate the ability of 6-OHDA to cause both lipid peroxidation and protein oxidation, with the latter including a reduction in free-thiol content and an increase in carbonyl content. Ascorbate also increases the lipid peroxidation induced by the action of copper and 6-OHDA. Glutathione protects against the copper-induced lipid peroxidation, but does not reduce its potential to oxidize free thiols. These results clearly demonstrate the potential of copper to increase the capacity of 6-OHDA to generate oxidative stress and the ability of ascorbate to enhance this potential, which may contribute to the destruction of dopaminergic neurons. © 2017 International Society for Neurochemistry.

Effect of Nano-Al₂O₃ on the Toxicity and Oxidative Stress of Copper towards Scenedesmus obliquus.

PubMed

Li, Xiaomin; Zhou, Suyang; Fan, Wenhong

2016-06-09

Nano-Al₂O₃ has been widely used in various industries; unfortunately, it can be released into the aquatic environment. Although nano-Al₂O₃ is believed to be of low toxicity, it can interact with other pollutants in water, such as heavy metals. However, the interactions between nano-Al₂O₃ and heavy metals as well as the effect of nano-Al₂O₃ on the toxicity of the metals have been rarely investigated. The current study investigated copper toxicity in the presence of nano-Al₂O₃ towards Scenedesmus obliquus. Superoxide dismutase activity and concentration of glutathione and malondialdehyde in cells were determined in order to quantify oxidative stress in this study. Results showed that the presence of nano-Al₂O₃ reduced the toxicity of Cu towards S. obliquus. The existence of nano-Al₂O₃ decreased the growth inhibition of S. obliquus. The accumulation of copper and the level of oxidative stress in algae were reduced in the presence of nano-Al₂O₃. Furthermore, lower copper accumulation was the main factor that mitigated copper toxicity with the addition of nano-Al₂O₃. The decreased copper uptake could be attributed to the adsorption of copper onto nanoparticles and the subsequent decrease of available copper in water.

Aluminium or copper substrate panel for selective absorption of solar energy

NASA Technical Reports Server (NTRS)

Roberts, M. L.; Sharpe, M. H.; Krupnick, A. C. (Inventor)

1979-01-01

A method for making panels which selectively absorb solar energy is disclosed. The panels are comprised of an aluminum substrate, a layer of zinc thereon, a layer of nickel over the zinc layer and an outer layer of solar energy absorbing nickel oxide or a copper substrate with a layer of nickel thereon and a layer of solar energy absorbing nickel oxide distal from the copper substrate.

Method for making an aluminum or copper substrate panel for selective absorption of solar energy

NASA Technical Reports Server (NTRS)

Roberts, M. L.; Sharpe, M. H.; Krupnick, A. C. (Inventor)

1978-01-01

A panel is described for selectively absorbing solar energy comprising an aluminum substrate. A zinc layer was covered by a layer of nickel and an outer layer of solar energy absorbing nickel oxide or a copper substrate with a nickel layer. A layer of solar energy absorbing nickel oxide distal from the copper substrate was included. A method for making these panels is disclosed.

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

DOE PAGES

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan; ...

2017-08-21

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

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

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

Chemically modified Moringa oleifera seed husks as low cost adsorbent for removal of copper from aqueous solution

NASA Astrophysics Data System (ADS)

Ghafar, Faridah; Mohtar, Aminullah; Sapawe, Norzahir; Hadi, Norulakmal Nor; Salleh, Marmy Roshaidah Mohd

2017-12-01

Moringa oleifera husks (MOH) are an agricultural byproduct that may have potential as adsorbent for removal of heavy metal ions in wastewater such as copper (Cu2+). The release of Cu2+ to the environment by the mining and electroplating industries cause a major problem because it is toxic and can cause liver and kidney problems. Hence, it is important to remove copper before the wastewater can be discharged to the environment. In order to increase the adsorption capacity, the MOH was chemically modified using citric acid. The raw and modified MOH were analyzed using Fourier Transform Infra-Red (FTIR) for identification of functional groups present at the adsorbent surface. The adsorption study was carried out using the batch technique in water bath shaker investigating different parameters; adsorbent dosage (30 - 70 g/L), initial concentration of copper (30 - 150 mg/L), contact time (2 - 90 min), temperature (27 - 60 °C) at constant agitation of 100 rpm. The concentrations of copper in aqueous solution before and after the adsorption process was analyzed using Atomic Absorption Spectrum (AAS). The highest percentage removal of copper was found at 10g/L of adsorbent dosage with 30 mg/L of initial concentration and temperature 30 °C. It was also observed that the adsorption of copper by MOH was approaching to equilibrium at 60 min of reaction time. From the FTIR analysis, it was found that the MOH contains hydroxyl, carboxyl and amine groups. The high adsorption capacity of modified MOH to remove copper from aqueous solution makes it preferable and attractive alternative to commercial adsorbent.

Impact on sediments and water by release of copper from chalcopyrite bearing rock due to acidic mine drainage

NASA Astrophysics Data System (ADS)

Shukla, Anoop Kant; Pradhan, Manoj; Tiwari, Onkar Nath

2018-04-01

Mining activity causes transition of rock-mass from its original position in earth into open environment. The action of environmental elements such air, water, microorganisms leads to oxidation of minerals which constitute the rock. The oxidation of sulphide minerals in presence of moisture releases acidic mine discharge (AMD). The acidic nature of AMD causes leaching of metals from rock minerals. Dissolution of other minerals may occur upon reaction with AMD. Chalcopyrite (CuFeS2) undergoes oxidation in acidic condition releasing copper among other products. This study reveals contamination of copper in sediment samples and seepage water from the tailing dam of a large copper project in located in central India. Elevation was studied using GIS to ascertain to the topographic elevation of tailing dam area. It was located at relatively high altitude causing seepage to flow away from tailing dam. The seepage water from tailing dam was found to be acidic with mean pH value of 4.0 and elevated copper content. Similarly, sediments from seepage water flow displayed elevated copper concentration. The copper concentration in seepage water was found with a mean value of 10.73 mg/l. The sediments from seepage water flow also displayed elevated copper concentration with mean value of 26.92 g/kg. This indicates impact on sediments by release of copper due to acidic mine drainage.

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

PubMed

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

2002-02-13

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

Release of copper from embedded solid copper bullets into muscle and fat tissues of fallow deer (Dama dama), roe deer (Capreolus capreolus), and wild boar (Sus scrofa) and effect of copper content on oxidative stability of heat-processed meat.

PubMed

Schuhmann-Irschik, I; Sager, M; Paulsen, P; Tichy, A; Bauer, F

2015-10-01

When venison with embedded copper bullets was subjected to different culinary processing procedures, the amount of copper released from the embedded bullet was affected more by the retention period of the bullet in the meat during cool storage, than by the different heating protocols. The presence of copper fragments had no significant effect on levels of thiobarbituric acid reactive substances (TBARS). Conversely, TBARS in lean meat (fallow deer, wild boar, roe deer) were significantly affected by culinary treatment (higher TBARS in boiled and boiled-stored meat than in meat barbecued or boiled in brine). In pork-beef patties doped with up to 28mg/kg Cu, TBARS increased after dry-heating and subsequently storing the meat patties. The amount of copper doping had no effect on TBARS for 0 and 7days of storage, but a significant effect at day 14 (fat oxidation retarded at higher Cu doses). Evidence is presented that wild boar meat may be more sensitive to fat oxidation than pork-beef. Copyright © 2015 Elsevier Ltd. All rights reserved.

In vitro inhibition of hyaluronidase by sodium copper chlorophyllin complex and chlorophyllin analogs

PubMed Central

McCook, John P; Dorogi, Peter L; Vasily, David B; Cefalo, Dustin R

2015-01-01

Background Inhibitors of hyaluronidase are potent agents that maintain hyaluronic acid homeostasis and may serve as anti-aging, anti-inflammatory, and anti-microbial agents. Sodium copper chlorophyllin complex is being used therapeutically as a component in anti-aging cosmeceuticals, and has been shown to have anti-hyaluronidase activity. In this study we evaluated various commercial lots of sodium copper chlorophyllin complex to identify the primary small molecule constituents, and to test various sodium copper chlorophyllin complexes and their small molecule analog compounds for hyaluronidase inhibitory activity in vitro. Ascorbate analogs were tested in combination with copper chlorophyllin complexes for potential additive or synergistic activity. Materials and methods For hyaluronidase activity assays, dilutions of test materials were evaluated for hydrolytic activity of hyaluronidase by precipitation of non-digested hyaluronate by measuring related turbidity at 595 nm. High-performance liquid chromatography and mass spectroscopy was used to analyze and identify the primary small molecule constituents in various old and new commercial lots of sodium copper chlorophyllin complex. Results The most active small molecule component of sodium copper chlorophyllin complex was disodium copper isochlorin e4, followed by oxidized disodium copper isochlorin e4. Sodium copper chlorophyllin complex and copper isochlorin e4 disodium salt had hyaluronidase inhibitory activity down to 10 µg/mL. The oxidized form of copper isochlorin e4 disodium salt had substantial hyaluronidase inhibitory activity at 100 µg/mL but not at 10 µg/mL. Ascorbate derivatives did not enhance the hyaluronidase inhibitory activity of sodium copper chlorophyllin. Copper isochlorin e4 analogs were always the dominant components of the small molecule content of the commercial lots tested; oxidized copper isochlorin e4 was found in increased concentrations in older compared to newer lots tested. Conclusion These results support the concept of using the hyaluronidase inhibitory activity of sodium copper chlorophyllin complex to increase the hyaluronic acid level of the dermal extracellular matrix for the improvement of the appearance of aging facial skin. PMID:26300653

In vitro inhibition of hyaluronidase by sodium copper chlorophyllin complex and chlorophyllin analogs.

PubMed

McCook, John P; Dorogi, Peter L; Vasily, David B; Cefalo, Dustin R

2015-01-01

Inhibitors of hyaluronidase are potent agents that maintain hyaluronic acid homeostasis and may serve as anti-aging, anti-inflammatory, and anti-microbial agents. Sodium copper chlorophyllin complex is being used therapeutically as a component in anti-aging cosmeceuticals, and has been shown to have anti-hyaluronidase activity. In this study we evaluated various commercial lots of sodium copper chlorophyllin complex to identify the primary small molecule constituents, and to test various sodium copper chlorophyllin complexes and their small molecule analog compounds for hyaluronidase inhibitory activity in vitro. Ascorbate analogs were tested in combination with copper chlorophyllin complexes for potential additive or synergistic activity. For hyaluronidase activity assays, dilutions of test materials were evaluated for hydrolytic activity of hyaluronidase by precipitation of non-digested hyaluronate by measuring related turbidity at 595 nm. High-performance liquid chromatography and mass spectroscopy was used to analyze and identify the primary small molecule constituents in various old and new commercial lots of sodium copper chlorophyllin complex. The most active small molecule component of sodium copper chlorophyllin complex was disodium copper isochlorin e4, followed by oxidized disodium copper isochlorin e4. Sodium copper chlorophyllin complex and copper isochlorin e4 disodium salt had hyaluronidase inhibitory activity down to 10 µg/mL. The oxidized form of copper isochlorin e4 disodium salt had substantial hyaluronidase inhibitory activity at 100 µg/mL but not at 10 µg/mL. Ascorbate derivatives did not enhance the hyaluronidase inhibitory activity of sodium copper chlorophyllin. Copper isochlorin e4 analogs were always the dominant components of the small molecule content of the commercial lots tested; oxidized copper isochlorin e4 was found in increased concentrations in older compared to newer lots tested. These results support the concept of using the hyaluronidase inhibitory activity of sodium copper chlorophyllin complex to increase the hyaluronic acid level of the dermal extracellular matrix for the improvement of the appearance of aging facial skin.

Generation of metallic plasmon nanostructures in a thin transparent photosensitive copper oxide film by femtosecond thermochemical decomposition

NASA Astrophysics Data System (ADS)

Danilov, P. A.; Zayarny, D. A.; Ionin, A. A.; Kudryashov, S. I.; Litovko, E. P.; Mel'nik, N. N.; Rudenko, A. A.; Saraeva, I. N.; Umanskaya, S. P.; Khmelnitskii, R. A.

2017-09-01

Irradiation of optically transparent copper (I) oxide film covering a glass substrate with a tightly focused femtosecond laser pulses in the pre-ablation regime leads to film reduction to a metallic colloidal state via a single-photon absorption and its subsequent thermochemical decomposition. This effect was demonstrated by the corresponding measurement of the extinction spectrum in visible spectral range. The laser-induced formation of metallic copper nanoparticles in the focal region inside the bulk oxide film allows direct recording of individual thin-film plasmon nanostructures and optical-range metasurfaces.

Current Status and Future Prospects of Copper Oxide Heterojunction Solar Cells.

PubMed

Wong, Terence K S; Zhuk, Siarhei; Masudy-Panah, Saeid; Dalapati, Goutam K

2016-04-07

The current state of thin film heterojunction solar cells based on cuprous oxide (Cu₂O), cupric oxide (CuO) and copper (III) oxide (Cu₄O₃) is reviewed. These p-type semiconducting oxides prepared by Cu oxidation, sputtering or electrochemical deposition are non-toxic, sustainable photovoltaic materials with application potential for solar electricity. However, defects at the copper oxide heterojunction and film quality are still major constraining factors for achieving high power conversion efficiency, η. Amongst the Cu₂O heterojunction devices, a maximum η of 6.1% has been obtained by using pulsed laser deposition (PLD) of Al x Ga 1- x O onto thermal Cu₂O doped with Na. The performance of CuO/n-Si heterojunction solar cells formed by magnetron sputtering of CuO is presently limited by both native oxide and Cu rich copper oxide layers at the heterointerface. These interfacial layers can be reduced by using a two-step sputtering process. A high η of 2.88% for CuO heterojunction solar cells has been achieved by incorporation of mixed phase CuO/Cu₂O nanopowder. CuO/Cu₂O heterojunction solar cells fabricated by electrodeposition and electrochemical doping has a maximum efficiency of 0.64% after surface defect passivation and annealing. Finally, early stage study of Cu₄O₃/GaN deposited on sapphire substrate has shown a photovoltaic effect and an η of ~10 -2 %.

Oxidation-Reduction Resistance of Advanced Copper Alloys

NASA Technical Reports Server (NTRS)

Greenbauer-Seng, L. (Technical Monitor); Thomas-Ogbuji, L.; Humphrey, D. L.; Setlock, J. A.

2003-01-01

Resistance to oxidation and blanching is a key issue for advanced copper alloys under development for NASA's next generation of reusable launch vehicles. Candidate alloys, including dispersion-strengthened Cu-Cr-Nb, solution-strengthened Cu-Ag-Zr, and ODS Cu-Al2O3, are being evaluated for oxidation resistance by static TGA exposures in low-p(O2) and cyclic oxidation in air, and by cyclic oxidation-reduction exposures (using air for oxidation and CO/CO2 or H2/Ar for reduction) to simulate expected service environments. The test protocol and results are presented.

Determination of adsorptive and catalytic properties of copper, silver and iron contain titanium-pillared bentonite for the removal bisphenol A from aqueous solution

NASA Astrophysics Data System (ADS)

Tomul, Fatma; Turgut Basoglu, Funda; Canbay, Hale

2016-01-01

Ti-pillared bentonite, Cu, Ag and Fe modified Ti-pillared bentonite and Cu/Ti- and Fe/Ti-mixed pillared bentonite were synthesized using different titanium sources by direct synthesis or by modification after synthesis. The effects of synthesis conditions on the surface characteristics, pore structure and acidity of the pillared bentonites were investigated by SEM⿿EDS, XPS, XRD, N2-adsorption/desorption and FTIR analyses before and after ammonia adsorption. The results of EDS, XPS and XRD analysis confirmed that titanium, copper, silver and iron were incorporated into the bentonite structure. In the XRD patterns, the formation of delaminated structure reflecting the non-parallel distribution of the bentonite layers by pillaring with Ti, Cu/Ti and Fe/Ti-pillars was observed. XPS spectra indicated the presence of TiO2, CuO, Ag and Ag2O and Fe2O3 species depending on the source of active metals in the synthesized samples. In the FTIR spectra, an increase in the Bronsted/Lewis peak intensity was observed with the loading of copper and iron, whereas a decrease in Lewis and Bronsted acidities was observed with incorporation of silver. Adsorption studies indicated that the adsorption capacity of the sample synthesized using titanium (IV) propoxide and incorporating iron to the structure by ion exchange (Fe-PTi-PILC) were higher than those in other samples. The adsorption of BPA (bisphenol A) by all tested samples was found to fit the Langmuir isotherm. In the catalytic wet peroxide oxidation (CWPO) over PTi-PILC (prepared by titanium (IV) propoxide), Fe-PTi-PILC and Cu-PTi-PILC (prepared by copper impregnated Ti-pillared bentonite) samples, BPA values close to complete conversion were achieved within 30 min at 25 °C, pH 4 and 5 g/L mcat. CWPO results showed that increasement of pH causes a decrease the rate of oxidation. On the other hand, by the time catalyst and BPA concentration is increased, the rate of oxidation is increased as well.

Flexible transparent conducting hybrid film using a surface-embedded copper nanowire network: a highly oxidation-resistant copper nanowire electrode for flexible optoelectronics.

PubMed

Im, Hyeon-Gyun; Jung, Soo-Ho; Jin, Jungho; Lee, Dasom; Lee, Jaemin; Lee, Daewon; Lee, Jung-Yong; Kim, Il-Doo; Bae, Byeong-Soo

2014-10-28

We report a flexible high-performance conducting film using an embedded copper nanowire transparent conducting electrode; this material can be used as a transparent electrode platform for typical flexible optoelectronic devices. The monolithic composite structure of our transparent conducting film enables simultaneously an outstanding oxidation stability of the copper nanowire network (14 d at 80 °C), an exceptionally smooth surface topography (R(rms) < 2 nm), and an excellent opto-electrical performances (Rsh = 25 Ω sq(-1) and T = 82%). A flexible organic light emitting diode device is fabricated on the transparent conducting film to demonstrate its potential as a flexible copper nanowire electrode platform.

Flavonoids and urate antioxidant interplay in plasma oxidative stress.

PubMed

Filipe, P; Lança, V; Silva, J N; Morlière, P; Santus, R; Fernandes, A

2001-05-01

Flavonoids are naturally occurring plant compounds with antioxidant properties. Their consumption has been associated with the protective effects of certain diets against some of the complications of atherosclerosis. Low-density lipoprotein (LDL) oxidative modification is currently thought to be a significant event in the atherogenic process. Most of the experiments concerning the inhibition of LDL oxidation used isolated LDL. We used diluted human whole plasma to study the influence of flavonoids on lipid peroxidation (LPO) promoted by copper, and their interaction with uric acid, one of the most important plasma antioxidants. Lipid peroxidation was evaluated by the formation of thiobarbituric acid reactive substances (TBARS) and of free malondialdehyde (MDA). The comparative capability of the assayed flavonoids on copper (II) reduction was tested using the neocuproine colorimetric test. In our assay system, urate disappears and free MDA and TBARS formation increase during the incubation of plasma with copper. Most of the tested flavonoids inhibited copper-induced LPO. The inhibition of LPO by flavonoids correlated positively with their capability to reduce copper (II). The urate consumption during the incubation of plasma with copper was inhibited by myricetin, quercetin and kaempferol. The inhibition of urate degradation by flavonoids correlated positively with the inhibition of LPO. Urate inhibited the copper-induced LPO in a concentration-dependent mode. Luteolin, rutin, catechin and quercetin had an antioxidant synergy with urate. Our results show that some flavonoids could protect endogenous urate from oxidative degradation, and demonstrate an antioxidant synergy between urate and some of the flavonoids.

Contributions of Stress and Oxidation on the Formation of Whiskers in Pb-free Solders

DTIC Science & Technology

2016-01-29

environmental factors influencing formation of tin whiskers on electrodeposited lead free, tin coatings over copper (or copper containing) substrates is the...Oxidation on the Formation of Whiskers in Pb‐free Solders,” WP-1754 15. SUBJECT TERMS Tin Whiskers, Residual Stress, Environmental Degradation 16...showing the surface of a tin film with whisker .................... 2 Figure 2: SEM Micrograph of Tin film on Copper Substrate cross-sectioned by FIB

Is copper chelation an effective anti-angiogenic strategy for cancer treatment?

PubMed

Antoniades, V; Sioga, A; Dietrich, E M; Meditskou, S; Ekonomou, L; Antoniades, K

2013-12-01

Angiogenesis and the acquisition of an angiogenic phenotype is important for cancer cell proliferation. Copper in an essential trace element that participates in many enzymatic complexes like the cytochrome c, superoxide dismutase and lysyl oxidase and it is involved in processes, like embryogenesis, growth, angiogenesis and carcinogenesis. In particular, its involvement in carcinogenesis was described for the first time in oral submucous fibrosis, where fibroblasts produce large amounts of collagen in the presence of copper. Copper's action in carcinogenesis is two-fold: (1) it participates in reactions with an increased redox potential that result in the production of oxidative products and oxidative stress. Through this mechanism, copper may cause DNA mutations in the nucleus and mitochondria or alterations to membrane phospholipids, (2) it participates in angiogenesis even in the absence of angiogenic molecules, as it was reported for the first time in rabbit cornea models with copolymer pellets charged with PGE1. Copper chelation regimens like penicillamine and tetrathiomolybdate are being described in the literature as having anti-angiogenic, anti-fibrotic and anti-inflammatory actions. Animal models of brain cancer that evaluated the anti-angiogenic properties of copper, have proven evidence of the reduction of tumor's microvascular supply, tumor volume and vascular permeability after plasma copper levels reduction. Interestingly, plasma copper levels reduction was shown to suppress micrometastases generation in mice models of breast cancer. We hypothesize that copper chelation therapy: increases oxidative stress in cancer cells to a level that does not allow survival because of the reduction of anti-oxidative enzymes production. It may also result in inhibition of angiogenesis and of the initiation of the angiogenic switch, because copper normally enhances endothelial cell migration and proliferation, improves binding of growth factors to endothelial cells and enhances the expression of angiogenic molecules. Copper chelation may also reduce extracellular matrix degradation and cancer spread, through reduction of MMP-9 production and probably of other collagenases and may inhibit propagation of micrometastases. However, copper chelation therapy may enhance angiogenesis through reduction of thrombospondin-1, that results into an increase in VEGF-VEGFR2 complexes and a high level of active MMP-9. These hypotheses help in understanding of the anti-angiogenic action of copper chelation therapies and of the complex network of interactions between copper and other molecules involved in angiogenesis. It may also stimulate further research regarding differences in copper metabolism, the effects of anti-copper regimens on organs, the development of resistance, and their possible angiogenic action through thrombospondin expression reduction. Copyright © 2013 Elsevier Ltd. All rights reserved.

Review of Fabrication Methods, Physical Properties, and Applications of Nanostructured Copper Oxides Formed via Electrochemical Oxidation.

PubMed

Stepniowski, Wojciech J; Misiolek, Wojciech Z

2018-05-29

Typically, anodic oxidation of metals results in the formation of hexagonally arranged nanoporous or nanotubular oxide, with a specific oxidation state of the transition metal. Recently, the majority of transition metals have been anodized; however, the formation of copper oxides by electrochemical oxidation is yet unexplored and offers numerous, unique properties and applications. Nanowires formed by copper electrochemical oxidation are crystalline and composed of cuprous (CuO) or cupric oxide (Cu₂O), bringing varied physical and chemical properties to the nanostructured morphology and different band gaps: 1.44 and 2.22 eV, respectively. According to its Pourbaix (potential-pH) diagram, the passivity of copper occurs at ambient and alkaline pH. In order to grow oxide nanostructures on copper, alkaline electrolytes like NaOH and KOH are used. To date, no systemic study has yet been reported on the influence of the operating conditions, such as the type of electrolyte, its temperature, and applied potential, on the morphology of the grown nanostructures. However, the numerous reports gathered in this paper will provide a certain view on the matter. After passivation, the formed nanostructures can be also post-treated. Post-treatments employ calcinations or chemical reactions, including the chemical reduction of the grown oxides. Nanostructures made of CuO or Cu₂O have a broad range of potential applications. On one hand, with the use of surface morphology, the wetting contact angle is tuned. On the other hand, the chemical composition (pure Cu₂O) and high surface area make such materials attractive for renewable energy harvesting, including water splitting. While compared to other fabrication techniques, self-organized anodization is a facile, easy to scale-up, time-efficient approach, providing high-aspect ratio one-dimensional (1D) nanostructures. Despite these advantages, there are still numerous challenges that have to be faced, including the strict control of the chemical composition and morphology of the grown nanostructures, their uniformity, and understanding the mechanism of their growth.

Pure and Oxidized Copper Materials as Potential Antimicrobial Surfaces for Spaceflight Activities.

PubMed

Hahn, C; Hans, M; Hein, C; Mancinelli, R L; Mücklich, F; Wirth, R; Rettberg, P; Hellweg, C E; Moeller, R

2017-12-01

Microbial biofilms can lead to persistent infections and degrade a variety of materials, and they are notorious for their persistence and resistance to eradication. During long-duration space missions, microbial biofilms present a danger to crew health and spacecraft integrity. The use of antimicrobial surfaces provides an alternative strategy for inhibiting microbial growth and biofilm formation to conventional cleaning procedures and the use of disinfectants. Antimicrobial surfaces contain organic or inorganic compounds, such as antimicrobial peptides or copper and silver, that inhibit microbial growth. The efficacy of wetted oxidized copper layers and pure copper surfaces as antimicrobial agents was tested by applying cultures of Escherichia coli and Staphylococcus cohnii to these metallic surfaces. Stainless steel surfaces were used as non-inhibitory control surfaces. The production of reactive oxygen species and membrane damage increased rapidly within 1 h of exposure on pure copper surfaces, but the effect on cell survival was negligible even after 2 h of exposure. However, longer exposure times of up to 4 h led to a rapid decrease in cell survival, whereby the survival of cells was additionally dependent on the exposed cell density. Finally, the release of metal ions was determined to identify a possible correlation between copper ions in suspension and cell survival. These measurements indicated a steady increase of free copper ions, which were released indirectly by cells presumably through excreted complexing agents. These data indicate that the application of antimicrobial surfaces in spaceflight facilities could improve crew health and mitigate material damage caused by microbial contamination and biofilm formation. Furthermore, the results of this study indicate that cuprous oxide layers were superior to pure copper surfaces related to the antimicrobial effect and that cell density is a significant factor that influences the time dependence of antimicrobial activity. Key Words: Contact killing-E. coli-S. cohnii-Antimicrobial copper surfaces-Copper oxide layers-Human health-Planetary protection. Astrobiology 17, 1183-1191.

Using Copper to Improve the Well-Being of the Skin

PubMed Central

Borkow, Gadi

2014-01-01

Copper has two key properties that are being exploited in consumer and medical device products in the last decade. On the one hand, copper has potent biocidal properties. On the other hand, copper is involved in numerous physiological and metabolic processes critical for the appropriate functioning of almost all tissues in the human body. In the skin, copper is involved in the synthesis and stabilization of extracellular matrix skin proteins and angiogenesis. This manuscript reviews clinical studies that show that the use of textile consumer and medical device products, embedded with microscopic copper oxide particles, improve the well-being of the skin. These include studies showing a) cure of athlete’s foot infections and improvement in skin elasticity, especially important for individuals suffering from diabetes; b) reduction of facial fine line and wrinkles; and c) enhancement of wound healing; by copper oxide embedded socks, pillowcases and wound dressings, respectively. The manuscript also reviews and discusses the mechanisms by which the presence of copper in these products improves skin well-being. PMID:26361585

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

PubMed

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

2016-08-01

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

Subchronic Toxicity of Copper Oxide Nanoparticles and Its Attenuation with the Help of a Combination of Bioprotectors

PubMed Central

Privalova, Larisa I.; Katsnelson, Boris A.; Loginova, Nadezhda V.; Gurvich, Vladimir B.; Shur, Vladimir Y.; Valamina, Irene E.; Makeyev, Oleg H.; Sutunkova, Marina P.; Minigalieva, Ilzira A.; Kireyeva, Ekaterina P.; Rusakov, Vadim O.; Tyurnina, Anastasia E.; Kozin, Roman V.; Meshtcheryakova, Ekaterina Y.; Korotkov, Artem V.; Shuman, Eugene A.; Zvereva, Anastasia E.; Kostykova, Svetlana V.

2014-01-01

In the copper metallurgy workplace air is polluted with condensation aerosols, which a significant fraction of is presented by copper oxide particles <100 nm. In the scientific literature, there is a lack of their in vivo toxicity characterization and virtually no attempts of enhancing organism’s resistance to their impact. A stable suspension of copper oxide particles with mean (±SD) diameter 20 ± 10 nm was prepared by laser ablation of pure copper in water. It was being injected intraperitoneally to rats at a dose of 10 mg/kg (0.5 mg per mL of deionized water) three times a week up to 19 injections. In parallel, another group of rats was so injected with the same suspension against the background of oral administration of a “bio-protective complex” (BPC) comprising pectin, a multivitamin-multimineral preparation, some amino acids and fish oil rich in ω-3 PUFA. After the termination of injections, many functional and biochemical indices for the organism’s status, as well as pathological changes of liver, spleen, kidneys, and brain microscopic structure were evaluated for signs of toxicity. In the same organs we have measured accumulation of copper while their cells were used for performing the Random Amplification of Polymorphic DNA (RAPD) test for DNA fragmentation. The same features were assessed in control rats infected intraperitoneally with water with or without administration of the BPC. The copper oxide nanoparticles proved adversely bio-active in all respects considered in this study, their active in vivo solubilization in biological fluids playing presumably an important role in both toxicokinetics and toxicodynamics. The BPC proposed and tested by us attenuated systemic and target organs toxicity, as well as genotoxicity of this substance. Judging by experimental data obtained in this investigation, occupational exposures to nano-scale copper oxide particles can present a significant health risk while the further search for its management with the help of innocuous bioprotectors seems to be justified. PMID:25026171

Subchronic toxicity of copper oxide nanoparticles and its attenuation with the help of a combination of bioprotectors.

PubMed

Privalova, Larisa I; Katsnelson, Boris A; Loginova, Nadezhda V; Gurvich, Vladimir B; Shur, Vladimir Y; Valamina, Irene E; Makeyev, Oleg H; Sutunkova, Marina P; Minigalieva, Ilzira A; Kireyeva, Ekaterina P; Rusakov, Vadim O; Tyurnina, Anastasia E; Kozin, Roman V; Meshtcheryakova, Ekaterina Y; Korotkov, Artem V; Shuman, Eugene A; Zvereva, Anastasia E; Kostykova, Svetlana V

2014-07-14

In the copper metallurgy workplace air is polluted with condensation aerosols, which a significant fraction of is presented by copper oxide particles<100 nm. In the scientific literature, there is a lack of their in vivo toxicity characterization and virtually no attempts of enhancing organism's resistance to their impact. A stable suspension of copper oxide particles with mean (±SD) diameter 20±10 nm was prepared by laser ablation of pure copper in water. It was being injected intraperitoneally to rats at a dose of 10 mg/kg (0.5 mg per mL of deionized water) three times a week up to 19 injections. In parallel, another group of rats was so injected with the same suspension against the background of oral administration of a "bio-protective complex" (BPC) comprising pectin, a multivitamin-multimineral preparation, some amino acids and fish oil rich in ω-3 PUFA. After the termination of injections, many functional and biochemical indices for the organism's status, as well as pathological changes of liver, spleen, kidneys, and brain microscopic structure were evaluated for signs of toxicity. In the same organs we have measured accumulation of copper while their cells were used for performing the Random Amplification of Polymorphic DNA (RAPD) test for DNA fragmentation. The same features were assessed in control rats infected intraperitoneally with water with or without administration of the BPC. The copper oxide nanoparticles proved adversely bio-active in all respects considered in this study, their active in vivo solubilization in biological fluids playing presumably an important role in both toxicokinetics and toxicodynamics. The BPC proposed and tested by us attenuated systemic and target organs toxicity, as well as genotoxicity of this substance. Judging by experimental data obtained in this investigation, occupational exposures to nano-scale copper oxide particles can present a significant health risk while the further search for its management with the help of innocuous bioprotectors seems to be justified.

Immobilization and release of copper species from a microstructured polypyrrole matrix.

PubMed

González, M B; Brugnoni, L I; Flamini, D O; Quinzani, L M; Saidman, S B

2017-01-01

Copper species immobilization in hollow rectangular-sectioned microtubes of polypyrrole (PPy) electrosynthesized on 316L stainless steel was carried out using two different methods. One of them involved the immobilization after the PPy electropolymerization and the other one during the electrosynthesis process. The electrodes modified with copper species were rotated at different speeds in well water under open-circuit potential conditions. The release of copper species from the PPy matrix and the antibacterial activity against Escherichia coli were analyzed. The obtained results demonstrate that the amount of copper species released as well as the bactericidal effects against E. coli increases with rotation speed. The PPy coating modified with copper species after the electropolymerization reaction exhibited the best performance in terms of antibacterial activity and corrosion protection. These electrodes were tested in a lab-scale continuous flow system for well water disinfection.

In vitro toxicological assessment of iron oxide, aluminium oxide and copper nanoparticles in prokaryotic and eukaryotic cell types.

PubMed

Sadiq, Rakhshinda; Khan, Qaiser Mahmood; Mobeen, Ameena; Hashmat, Amer Jamal

2015-04-01

Metallic nanoparticles (NPs) have a variety of applications in different industries including pharmaceutical industry where these NPs are used mainly for image analysis and drug delivery. The increasing interest in nanotechnology is largely associated with undefined risks to the human health and to the environment. Therefore, in the present study cytotoxic and genotoxic effects of iron oxide, aluminium oxide and copper nanoparticles were evaluated using most commonly used assays i.e. Ames assay, in vitro cytotoxicity assay, micronucleus assay and comet assay. Cytotoxicity to bacterial cells was assessed in terms of colony forming units by using Escherichia coli (gram negative) and Bacillus subtilis (gram positive). Ames assay was carried out using two bacterial strains of Salmonella typhimurium TA98 and TA100. Genotoxicity of these NPs was evaluated following exposure to monkey kidney cell line, CHS-20. No cytotoxic and genotoxic effects were observed for iron oxide, and aluminium oxide NPs. Copper NPs were found mutagenic in TA98 and in TA100 and also found cytotoxic in dose dependent manner. Copper NPs induced significant (p < 0.01) increase in number of binucleated cells with micronuclei (96.6 ± 5.40) at the highest concentration (25 µg/mL). Copper NPs also induced DNA strand breaks at 10 µg/mL and oxidative DNA damage at 5 and 10 µg/mL. We consider these findings very useful in evaluating the genotoxic potential of NPs especially because of their increasing applications in human health and environment with limited knowledge of their toxicity and genotoxicity.

Copper and Copper Proteins in Parkinson's Disease

PubMed Central

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

2014-01-01

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

Protective Effects of Lactobacillus plantarum CCFM8246 against Copper Toxicity in Mice

PubMed Central

Li, Xiaoxiao; Zhai, Qixiao; Wang, Gang; Zhang, Qiuxiang; Zhang, Hao; Chen, Wei

2015-01-01

Lactobacillus plantarum CCFM8246, which has a relatively strong copper binding capacity and tolerance to copper ions, was obtained by screening from 16 lactic acid bacteria in vitro. The selected strain was then applied to a mouse model to evaluate its protective function against copper intoxication in vivo. The experimental mice were divided into an intervention group and a therapy group; mice in the intervention group received co-administration of CCFM8246 and a copper ion solution by gavage, while mice in the therapy group were treated with CCFM8246 after 4 weeks of copper exposure. In both two groups, mice treated with copper alone and that treated with neither CCFM8246 nor copper served as positive and negative controls, respectively. At the end of the experimental period, the copper content in feces and tissues, the activity of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) in serum, and oxidation stress indices in liver and kidney tissue were determined. Learning and memory ability was evaluated by Morris water maze experiments. The results indicated that treatment with CCFM8246 significantly increased the copper content in feces to promote copper excretion, reduce the accumulation of copper in tissues, reverse oxidative stress induced by copper exposure, recover the ALT and AST in serum and improve the spatial memory of mice. PMID:26605944

Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

PubMed

Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

2016-12-19

We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-containing zeolite catalysts

DOEpatents

Price, G.L.; Kanazirev, V.

1996-12-10

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

Copper-containing zeolite catalysts

DOEpatents

Price, Geoffrey L.; Kanazirev, Vladislav

1996-01-01

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

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide.

PubMed

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-11-16

The effect of oxide coating on the activity of a copper-zinc oxide-based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO₂ conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides.

Quantitative analysis of oxygen content in copper oxide films using ultra microbalance

NASA Astrophysics Data System (ADS)

Shu, Yonghua; Wang, Lianhong; Liu, Chong; Fan, Jing

2014-12-01

Copper oxide films were prepared on quartz substrates through electron beam physical vapor deposition in a vacuum chamber, and the films were observed using X-ray diffraction (XRD) and scanning electron microscope (SEM). The oxygen content of the films were analyzed using an ultra microbalance. Results indicated that when the substrate was heated to 600°C and the oxygen flow rate was 5 sccm, the film was composed of 47% Cu and 53% Cu2O (mass percent), and the oxidation ratio of copper was 25%. After the deposition process at the same condition, i.e. the substrate at temperature of 600°C and blowed by oxygen flowrate of 5 sccm, then in-stu annealed at 600°C in low oxygen pressure of 10 Pa for 30 minutes, the film composition became 22% Cu2O and 78% CuO (mass percent), and the oxidation ratio of copper greatly increased to about 88%.

Iron Recovery from Copper Slag Through Oxidation-Reduction Magnetic Concentration at Intermediate Temperature

NASA Astrophysics Data System (ADS)

Wu, Zhiwen; Chen, Chen; Feng, Yahui; Hong, Xin

Large amounts of copper slag containing about 40 wt% iron is generated during the process of producing copper. Recovery of iron from the copper slag is very essential not only for recycling the valuable metals and mineral resources but also for protecting the environment. The purpose of this study was to investigate the possibility of separating fayalite by oxidation-reduction process into Magnetite and silicate phases in intermediate temperature condition. Experimental results show that when the oxidation reaction at 1000°C for 120min and the oxygen flow is 0.1L/min, most fayalite decompose to hematite, less part of magnetite and silica. And then, the mixture of carbon and oxidation product is pressed into blocks and reduced to magnetite and silica at 900°C for 90min. A magnetic product containing about 57.9wt% iron was obtained from the magnetic separation under a magnetic field strength of 100 mT.

Nonenzymatic amperometric determination of glucose by CuO nanocubes-graphene nanocomposite modified electrode.

PubMed

Luo, Liqiang; Zhu, Limei; Wang, Zhenxin

2012-12-01

Here, we report a nonenzymatic amperometric glucose sensor based on copper oxide (CuO) nanocubes-graphene nanocomposite modified glassy carbon electrode (CuO-G-GCE). In this case, the graphene sheets were cast on the GCE directly. CuO nanocubes were obtained by oxidizing electrochemically deposited Cu on the graphene. The morphology of CuO-G nanocomposite was characterized by scanning electron microscopy. The CuO-G-GCE-based sensor exhibited excellent electrocatalytic activity and high stability for glucose oxidation. Under optimized conditions, the linearity between the current response and the glucose concentration was obtained in the range of 2μM to 4mM with a detection limit of 0.7μM (S/N=3), and a high sensitivity of 1360μAmM(-1)cm(-2). The proposed electrode showed a fast response time (less than 5s) and a good reproducibility. The as-made sensor was applied to determine the glucose levels in clinic human serum samples with satisfactory results. In addition, the effects of common interfering species, including ascorbic acid, uric acid, dopamine and other carbohydrates, on the amperometric response of the sensor were investigated and discussed in detail. Copyright © 2012 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2013-01-01

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

Effect of Nano-Al2O3 on the Toxicity and Oxidative Stress of Copper towards Scenedesmus obliquus

PubMed Central

Li, Xiaomin; Zhou, Suyang; Fan, Wenhong

2016-01-01

Nano-Al2O3 has been widely used in various industries; unfortunately, it can be released into the aquatic environment. Although nano-Al2O3 is believed to be of low toxicity, it can interact with other pollutants in water, such as heavy metals. However, the interactions between nano-Al2O3 and heavy metals as well as the effect of nano-Al2O3 on the toxicity of the metals have been rarely investigated. The current study investigated copper toxicity in the presence of nano-Al2O3 towards Scenedesmus obliquus. Superoxide dismutase activity and concentration of glutathione and malondialdehyde in cells were determined in order to quantify oxidative stress in this study. Results showed that the presence of nano-Al2O3 reduced the toxicity of Cu towards S. obliquus. The existence of nano-Al2O3 decreased the growth inhibition of S. obliquus. The accumulation of copper and the level of oxidative stress in algae were reduced in the presence of nano-Al2O3. Furthermore, lower copper accumulation was the main factor that mitigated copper toxicity with the addition of nano-Al2O3. The decreased copper uptake could be attributed to the adsorption of copper onto nanoparticles and the subsequent decrease of available copper in water. PMID:27294942

Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: an efficient method for the preparation of oxygen isotopically labeled carbonyl compounds.

PubMed

Shibahara, Fumitoshi; Suenami, Aiko; Yoshida, Atsunori; Murai, Toshiaki

2007-06-21

A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative.

Determining Prehistoric Mining Practices in Southeastern Europe Using Copper Isotopes

NASA Astrophysics Data System (ADS)

Powell, Wayne; Mathur, Ryan; Bankoff, H. Arthur; Bulatović, Aleksandar; Filipović, Vojislav

2017-04-01

Copper was first smelted from malachite at 5000 BCE in Serbia. There the Eneolithic (Copper Age) began with the production of small jewelry pieces and progressed to the casting of massive copper tools near its end, approximately 2000 years later. However, copper metallurgy in southeastern Europe ceased or significantly decreased in the later third millennium, several centuries before the Bronze Age began. Whether this metallurgical hiatus was the result a cultural shift or depletion of natural resources remains an ongoing subject of debate. It has been speculated that the marked reduction in metal production at the Eneolithic-Bronze Age transition was due to the exhaustion of surficial weathered oxide ores and the technical inability to smelt the underlying sulfide minerals. The behavior of copper isotopes in near-surface environments allows us to differentiate highly weathered oxide ores that occur at Earth's surface from non-weathered sulfide ores that occur at greater depth. The oxidation of copper generates fluids and associated minerals that are enriched in the 65Cu isotope. Thus, oxidative weathering of sulfide ores leads to the development of three stratified isotopic reservoirs for copper: 1) oxides above the water table that are enriched in 65Cu; 2) residual weathered sulfides minerals at the water table that are depleted in 65Cu; and 3) non-fractionated, non-weathered sulfide ore below the water table. And so, the transformative shift to sulfide-based metallurgy will be delineated by a significant decrease in δ65Cu in copper artifacts corresponding to the first use of 65Cu-depleted residual ore. The degree of variability of primary ore composition from numerable ore deposits would likely result in the overlap of copper isotope composition between populations of artifacts. Therefore, shifts in the mean copper isotope values and associated standard deviations would best reflect changes in ores use. A baseline value of -0.2‰ ±0.5 (1) was determined from an average of 164 published measurements from chalcopyrite and bornite from 8 epithermal and massive sulfide deposits. Twenty-two (88%) of Eneolithic artifacts (n=25) have values greater than this, whereas eight (73%) of the Early Bronze age artifacts (n=11) yield compositions less than -0.2‰. The mean of Middle Bronze Age, Late Bronze Age and Early Iron Age (n=86) cluster near -0.2‰. This pattern is consistent with a progression to the mining of ore assemblages from increasing depths through prehistory. The shift from 65Cu-enriched to 65Cu-depleted copper in artifacts across the Eneolithic-Bronze Age boundary at 2500 BCE indicates that accessible near-surface oxide ore reserves were depleted after approximately two millennia of mining, and that the beginning of the Bronze Age in the Balkans corresponded to the acquisition of pyrotechnology which allowed for the extraction of metals from sulfide minerals and the resumption of copper mining activity in the region.

Additive-mediated electrochemical synthesis of platelike copper crystals for methanol electrooxidation.

PubMed

Venkatasubramanian, Rajesh; He, Jibao; Johnson, Michael W; Stern, Ilan; Kim, Dae Ho; Pesika, Noshir S

2013-10-29

A room-temperature electrochemical approach to synthesizing anisotropic platelike copper microcrystals and nanocrystals in the presence of potassium bromide is presented. Morphological and elemental characterization was performed using SEM, TEM, and XRD to confirm the anisotropic morphology and crystal structure of the synthesized copper particles. A possible mechanism for explaining the anisotropic crystal growth is proposed on the basis of the preferential adsorption of bromide ions to selective crystal faces. The shape-dependent electrocatalytic property of copper particles is demonstrated by its enhanced catalytic activity for methanol oxidation. Further development of such anisotropic copper particles localized on an electrode surface will lead us to find a suitable alternative for noble metal-based electrocatalysts for the methanol oxidation reaction relevant to fuel cells.

Improvisation of mechanical and electrical properties of Cu by reinforcing MWCNT using modified electro-co-deposition process

NASA Astrophysics Data System (ADS)

Belgamwar, Sachin U.; Sharma, N. N.

2018-04-01

Multi-walled Carbon nanotubes–copper (MWCNT/Cu) composite powders with variable MWCNT content were synthesized by modified electro-co-deposition method. The electro-co-deposited MWCNT/Cu powders were consolidated by conventional compaction and sintering process. The consolidated products were then hot rolled and cold drawn to fine wires. The MWCNT/Cu composite wire samples were characterized for electrical and mechanical properties. We have been able to achieve an increase of around 8% in electrical conductivity of the form wires repeatedly. It has been observed that there was gradual improvement in the properties with reinforcement of MWCNT in the copper matrix. The betterment of electrical property has been achieved with simultaneous improvement in mechanical properties of the wire. The yield strength of MWCNT/Cu composite wire was found to be four times and the tensile strength two times greater than that of pure copper. The improved properties are attributed to the proper distribution of MWCNTs in the copper matrix and excellent interfacial bonding between MWCNT and composite copper fabricated by the modified method.

Visualizing the Cu/Cu2(O) Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy.

PubMed

LaGrow, Alec P; Ward, Michael R; Lloyd, David C; Gai, Pratibha L; Boyes, Edward D

2017-01-11

Understanding the oxidation and reduction mechanisms of catalytically active transition metal nanoparticles is important to improve their application in a variety of chemical processes. In nanocatalysis the nanoparticles can undergo oxidation or reduction in situ, and thus the redox species are not what are observed before and after reactions. We have used the novel environmental scanning transmission electron microscope (ESTEM) with 0.1 nm resolution in systematic studies of complex dynamic oxidation and reduction mechanisms of copper nanoparticles. The oxidation of copper has previously been reported to be dependent on its crystallography and its interaction with the substrate. By following the dynamic oxidation process in situ in real time with high-angle annular dark-field imaging in the ESTEM, we use conditions ideal to track the oxidation front as it progresses across a copper nanoparticle by following the changes in the atomic number (Z) contrast with time. The oxidation occurs via the nucleation of the oxide phase (Cu 2 O) from one area of the nanoparticle which then progresses unidirectionally across the particle, with the Cu-to-Cu 2 O interface having a relationship of Cu{111}//Cu 2 O{111}. The oxidation kinetics are related to the temperature and oxygen pressure. When the process is reversed in hydrogen, the reduction process is observed to be similar to the oxidation, with the same crystallographic relationship between the two phases. The dynamic observations provide unique insights into redox mechanisms which are important to understanding and controlling the oxidation and reduction of copper-based nanoparticles.

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

PubMed Central

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

2017-01-01

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

Yeast and Mammalian Metallothioneins Functionally Substitute for Yeast Copper-Zinc Superoxide Dismutase

NASA Astrophysics Data System (ADS)

Tamai, Katherine T.; Gralla, Edith B.; Ellerby, Lisa M.; Valentine, Joan S.; Thiele, Dennis J.

1993-09-01

Copper-zinc superoxide dismutase catalyzes the disproportionation of superoxide anion to hydrogen peroxide and dioxygen and is thought to play an important role in protecting cells from oxygen toxicity. Saccharomyces cerevisiae strains lacking copper-zinc superoxide dismutase, which is encoded by the SOD1 gene, are sensitive to oxidative stress and exhibit a variety of growth defects including hypersensitivity to dioxygen and to superoxide-generating drugs such as paraquat. We have found that in addition to these known phenotypes, SOD1-deletion strains fail to grow on agar containing the respiratory carbon source lactate. We demonstrate here that expression of the yeast or monkey metallothionein proteins in the presence of copper suppresses the lactate growth defect and some other phenotypes associated with SOD1-deletion strains, indicating that copper metallothioneins substitute for copper-zinc superoxide dismutase in vivo to protect cells from oxygen toxicity. Consistent with these results, we show that yeast metallothionein mRNA levels are dramatically elevated under conditions of oxidative stress. Furthermore, in vitro assays demonstrate that yeast metallothionein, purified or from whole-cell extracts, exhibits copper-dependent antioxidant activity. Taken together, these data suggest that both yeast and mammalian metallothioneins may play a direct role in the cellular defense against oxidative stress by functioning as antioxidants.

Current Status and Future Prospects of Copper Oxide Heterojunction Solar Cells

PubMed Central

Wong, Terence K. S.; Zhuk, Siarhei; Masudy-Panah, Saeid; Dalapati, Goutam K.

2016-01-01

The current state of thin film heterojunction solar cells based on cuprous oxide (Cu2O), cupric oxide (CuO) and copper (III) oxide (Cu4O3) is reviewed. These p-type semiconducting oxides prepared by Cu oxidation, sputtering or electrochemical deposition are non-toxic, sustainable photovoltaic materials with application potential for solar electricity. However, defects at the copper oxide heterojunction and film quality are still major constraining factors for achieving high power conversion efficiency, η. Amongst the Cu2O heterojunction devices, a maximum η of 6.1% has been obtained by using pulsed laser deposition (PLD) of AlxGa1−xO onto thermal Cu2O doped with Na. The performance of CuO/n-Si heterojunction solar cells formed by magnetron sputtering of CuO is presently limited by both native oxide and Cu rich copper oxide layers at the heterointerface. These interfacial layers can be reduced by using a two-step sputtering process. A high η of 2.88% for CuO heterojunction solar cells has been achieved by incorporation of mixed phase CuO/Cu2O nanopowder. CuO/Cu2O heterojunction solar cells fabricated by electrodeposition and electrochemical doping has a maximum efficiency of 0.64% after surface defect passivation and annealing. Finally, early stage study of Cu4O3/GaN deposited on sapphire substrate has shown a photovoltaic effect and an η of ~10−2%. PMID:28773398

Simultaneous determination of epinephrene and paracetamol at copper-cobalt oxide spinel decorated nanocrystalline zeolite modified electrodes.

PubMed

Samanta, Subhajyoti; Srivastava, Rajendra

2016-08-01

In this study, CuCo2O4 and CuCo2O4 decorated nanocrystalline ZSM-5 materials were prepared. For comparative study, a series of MCo2O4 spinels were also prepared. Materials were characterized by the complementary combination of X-ray diffraction, N2-adsorption, UV-visible, and electron microscopic techniques. A simple and rapid method for the simultaneous determination of paracetamol and epinephrine at MCo2O4 spinels modified electrodes is presented in this manuscript. Among the materials investigated in this study, CuCo2O4 decorated nanocrystalline ZSM-5 exhibited the highest electrocatalytic activity with excellent stability, sensitivity, and selectivity. Analytical performance of the sensor was demonstrated in the determination of epinephrine and paracetamol in the commercial pharmaceutical samples. Copyright © 2016 Elsevier Inc. All rights reserved.

Electrical property heterogeneity at transparent conductive oxide/organic semiconductor interfaces: mapping contact ohmicity using conducting-tip atomic force microscopy.

PubMed

MacDonald, Gordon A; Veneman, P Alexander; Placencia, Diogenes; Armstrong, Neal R

2012-11-27

We demonstrate mapping of electrical properties of heterojunctions of a molecular semiconductor (copper phthalocyanine, CuPc) and a transparent conducting oxide (indium-tin oxide, ITO), on 20-500 nm length scales, using a conductive-probe atomic force microscopy technique, scanning current spectroscopy (SCS). SCS maps are generated for CuPc/ITO heterojunctions as a function of ITO activation procedures and modification with variable chain length alkyl-phosphonic acids (PAs). We correlate differences in small length scale electrical properties with the performance of organic photovoltaic cells (OPVs) based on CuPc/C(60) heterojunctions, built on these same ITO substrates. SCS maps the "ohmicity" of ITO/CuPc heterojunctions, creating arrays of spatially resolved current-voltage (J-V) curves. Each J-V curve is fit with modified Mott-Gurney expressions, mapping a fitted exponent (γ), where deviations from γ = 2.0 suggest nonohmic behavior. ITO/CuPc/C(60)/BCP/Al OPVs built on nonactivated ITO show mainly nonohmic SCS maps and dark J-V curves with increased series resistance (R(S)), lowered fill-factors (FF), and diminished device performance, especially near the open-circuit voltage. Nearly optimal behavior is seen for OPVs built on oxygen-plasma-treated ITO contacts, which showed SCS maps comparable to heterojunctions of CuPc on clean Au. For ITO electrodes modified with PAs there is a strong correlation between PA chain length and the degree of ohmicity and uniformity of electrical response in ITO/CuPc heterojunctions. ITO electrodes modified with 6-8 carbon alkyl-PAs show uniform and nearly ohmic SCS maps, coupled with acceptable CuPc/C(60)OPV performance. ITO modified with C14 and C18 alkyl-PAs shows dramatic decreases in FF, increases in R(S), and greatly enhanced recombination losses.

Virgin olive oil blended polyurethane micro/nanofibers ornamented with copper oxide nanocrystals for biomedical applications.

PubMed

Amna, Touseef; Hassan, M Shamshi; Yang, Jieun; Khil, Myung-Seob; Song, Ki-Duk; Oh, Jae-Don; Hwang, Inho

2014-01-01

Recently, substantial interest has been generated in using electrospun biomimetic nanofibers of hybrids, particularly organic/inorganic, to engineer different tissues. The present work, for the first time, introduced a unique natural and synthetic hybrid micronanofiber wound dressing, composed of virgin olive oil/copper oxide nanocrystals and polyurethane (PU), developed via facile electrospinning. The as-spun organic/inorganic hybrid micronanofibers were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis, X-ray diffraction, electron probe microanalysis, and transmission electron microscopy. The interaction of cells with scaffold was studied by culturing NIH 3T3 fibroblasts on an as-spun hybrid micronanofibrous mat, and viability, proliferation, and growth were assessed. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay results and SEM observation showed that the hybrid micronanofibrous scaffold was noncytotoxic to fibroblast cell culture and was found to benefit cell attachment and proliferation. Hence our results suggest the potential utilization of as-spun micronanoscaffolds for tissue engineering. Copper oxide-olive oil/PU wound dressing may exert its positive beneficial effects at every stage during wound-healing progression, and these micronanofibers may serve diverse biomedical applications, such as tissue regeneration, damaged skin treatment, wound healing applications, etc. Conclusively, the fabricated olive oil-copper oxide/PU micronanofibers combine the benefits of virgin olive oil and copper oxide, and therefore hold great promise for biomedical applications in the near future.

New biosensor for detection of copper ions in water based on immobilized genetically modified yeast cells.

PubMed

Vopálenská, Irena; Váchová, Libuše; Palková, Zdena

2015-10-15

Contamination of water by heavy metals represents a potential risk for both aquatic and terrestrial organisms, including humans. Heavy metals in water resources can come from various industrial activities, and drinking water can be ex-post contaminated by heavy metals such as Cu(2+) from house fittings (e.g., water reservoirs) and pipes. Here, we present a new copper biosensor capable of detecting copper ions at concentrations of 1-100 μM. This biosensor is based on cells of a specifically modified Saccharomyces cerevisiae strain immobilized in alginate beads. Depending on the concentration of copper, the biosensor beads change color from white, when copper is present in concentrations below the detection limit, to pink or red based on the increase in copper concentration. The biosensor was successfully tested in the determination of copper concentrations in real samples of water contaminated with copper ions. In contrast to analytical methods or other biosensors based on fluorescent proteins, the newly designed biosensor does not require specific equipment and allows the quick detection of copper in many parallel samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of the surface speciation on biofilm attachment to chalcopyrite by Acidithiobacillus thiooxidans.

PubMed

Lara, René H; García-Meza, J Viridiana; González, Ignacio; Cruz, Roel

2013-03-01

Surfaces of massive chalcopyrite (CuFeS2) electrodes were modified by applying variable oxidation potential pulses under growth media in order to induce the formation of different secondary phases (e.g., copper-rich polysulfides, S n(2-); elemental sulfur, S(0); and covellite, CuS). The evolution of reactivity (oxidation capacity) of the resulting chalcopyrite surfaces considers a transition from passive or inactive (containing CuS and S n(2-)) to active (containing increasing amounts of S(0)) phases. Modified surfaces were incubated with cells of sulfur-oxidizing bacteria (Acidithiobacillus thiooxidans) for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the density of cells attached to chalcopyrite surfaces, the structure of the formed biofilm, and their exopolysaccharides and nucleic acids were analyzed by confocal laser scanning microscopy (CLSM) and scanning electron microscopy coupled to dispersive X-ray analysis (SEM-EDS). Additionally, CuS and S n(2-)/S(0) speciation, as well as secondary phase evolution, was carried out on biooxidized and abiotic chalcopyrite surfaces using Raman spectroscopy and SEM-EDS. Our results indicate that oxidized chalcopyrite surfaces initially containing inactive S n(2-) and S n(2-)/CuS phases were less colonized by A. thiooxidans as compared with surfaces containing active phases (mainly S(0)). Furthermore, it was observed that cells were partially covered by CuS and S(0) phases during biooxidation, especially at highly oxidized chalcopyrite surfaces, suggesting the innocuous effect of CuS phases during A. thiooxidans performance. These results may contribute to understanding the effect of the concomitant formation of refractory secondary phases (as CuS and inactive S n(2-)) during the biooxidation of chalcopyrite by sulfur-oxidizing microorganisms in bioleaching systems.

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

DOEpatents

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

Luminescence properties of the dinuclear copper complex in the active site of hemocyanins.

PubMed

Beltramini, M; di Muro, P; Rocco, G P; Salvato, B

1994-09-01

The deoxygenated form of hemocyanin, containing a dinuclear Cu(I) active site, emits luminescence in the red with maximum around 1.54 microns-1 (650 nm). The luminescence of deoxyhemocyanin (deoxy-Hc) from arthropod species is detectable at room temperature, the quantum yield being 2.4-2.7 x 10(-3); in contrast, the emission from molluscan proteins can be detected only at liquid nitrogen temperature. The luminescence emission is an inherent property of the bis[Cu(I)-(histidine)3] complex of the deoxygenated form of the protein to which both Cu(I) ions contribute equally to the overall emission. Luminescence is not observed with the oxygenated and the oxidized forms of hemocyanin, in which the metal is in the Cu(II) state, and in the metal-depleted or apo-Hc form. Based on steady-state and time-resolved measurements and references to Cu(I) model compounds, the luminescence emission is attributed to a triplet excited state of a Cu(I)-to-N (histidine) charge transfer transition 3d-pi*. Acrylamide quenching experiments indicate that the metal active site is very shielded from the solvent. This property of deoxy-Hc enables us to directly follow reactions that modify either the copper oxidation number or the metal-to-protein stoichiometry.

Orienting the Microstructure Evolution of Copper Phthalocyanine as an Anode Interlayer in Inverted Polymer Solar Cells for High Performance.

PubMed

Li, Zhiqi; Liu, Chunyu; Zhang, Xinyuan; Li, Shujun; Zhang, Xulin; Guo, Jiaxin; Guo, Wenbin; Zhang, Liu; Ruan, Shengping

2017-09-20

Recent advances in the interfacial modification of inverted-type polymer solar cells (PSCs) have resulted from controlling the surface energy of the cathode-modified layer (TiO 2 or ZnO) to enhance the short-circuit current (J sc ) or optimizing the contact morphology of the cathode (indium tin oxide or fluorine-doped tin oxide) and active layer to increase the fill factor. Herein, we report that the performance enhancement of PSCs is achieved by incorporating a donor macromolecule copper phthalocyanine (CuPc) as an anode modification layer. Using the approach based on orienting the microstructure evolution, uniformly dispersed island-shaped CuPc spot accumulations are built on the top of PTB7:PC 71 BM blend film, leading to an efficient spectral absorption and photogenerated exciton splitting. The best power conversion efficiency of PSCs is increased up to 9.726%. In addition to the enhanced light absorption, the tailored anode energy level alignment and optimized boundary morphology by incorporating the CuPc interlayer boost charge extraction efficiency and suppress the interfacial molecular recombination. These results demonstrate that surface morphology induction through molecular deposition is an effective method to improve the performance of PSCs, which reveals the potential implications of the interlayer between the organic active layer and the electrode buffer layer.

Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

NASA Technical Reports Server (NTRS)

Heinemann, K.; Rao, D. B.; Douglass, D. L.

1975-01-01

Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

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

DOE PAGES

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

2016-06-03

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

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

PubMed

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

2016-06-03

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

Stability of boron-doped graphene/copper interface: DFT, XPS and OSEE studies

NASA Astrophysics Data System (ADS)

Boukhvalov, D. W.; Zhidkov, I. S.; Kukharenko, A. I.; Slesarev, A. I.; Zatsepin, A. F.; Cholakh, S. O.; Kurmaev, E. Z.

2018-05-01

Two different types of boron-doped graphene/copper interfaces synthesized using two different flow rates of Ar through the bubbler containing the boron source were studied. X-ray photoelectron spectra (XPS) and optically stimulated electron emission (OSEE) measurements have demonstrated that boron-doped graphene coating provides a high corrosion resistivity of Cu-substrate with the light traces of the oxidation of carbon cover. The density functional theory calculations suggest that for the case of substitutional (graphitic) boron-defect only the oxidation near boron impurity is energetically favorable and creation of the vacancies that can induce the oxidation of copper substrate is energetically unfavorable. In the case of non-graphitic boron defects oxidation of the area, a nearby impurity is metastable that not only prevent oxidation but makes boron-doped graphene. Modeling of oxygen reduction reaction demonstrates high catalytic performance of these materials.

Powder-Derived High-Conductivity Coatings for Copper Alloys

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, Linus U.

2003-01-01

Makers of high-thermal-flux engines prefer copper alloys as combustion chamber liners, owing to a need to maximize heat dissipation. Since engine environments are strongly oxidizing in nature and copper alloys generally have inadequate resistance to oxidation, the liners need coatings for thermal and environmental protection; however, coatings must be chosen with great care in order to avoid significant impairment of thermal conductivity. Powder-derived chromia- and alumina- forming alloys are being studied under NASA's programs for advanced reusable launch vehicles to succeed the space shuttle fleet. NiCrAlY and Cu-Cr compositions optimized for high thermal conductivity have been tested for static and cyclic oxidation, and for susceptibility to blanching - a mode of degradation arising from oxidation-reduction cycling. The results indicate that the decision to coat the liners or not, and which coating/composition to use, depends strongly on the specific oxidative degradation mode that prevails under service conditions.

Copper(II)-catalyzed electrophilic amination of quinoline N-oxides with O-benzoyl hydroxylamines.

PubMed

Li, Gang; Jia, Chunqi; Sun, Kai; Lv, Yunhe; Zhao, Feng; Zhou, Kexiao; Wu, Hankui

2015-03-21

Copper acetate-catalyzed C-H bond functionalization amination of quinoline N-oxides was achieved using O-benzoyl hydroxylamine as an electrophilic amination reagent, thereby affording the desired products in moderate to excellent yields. Electrophilic amination can also be performed in good yield on a gram scale.

Experimental Consequences of Mottness in High-Temperature Copper-Oxide Superconductors

ERIC Educational Resources Information Center

Chakraborty, Shiladitya

2009-01-01

It has been more than two decades since the copper-oxide high temperature superconductors were discovered. However, building a satisfactory theoretical framework to study these compounds still remains one of the major challenges in condensed matter physics. In addition to the mechanism of superconductivity, understanding the properties of the…

Antistatic Polycarbonate/Copper Oxide Composite

NASA Technical Reports Server (NTRS)

Kovich, Michael; Rowland, George R., Jr.

2003-01-01

A composite material consisting of polycarbonate filled with copper oxide has been found to be suitable as an antistatic material. This material was developed to satisfy a requirement for an antistatic material that has a mass density less than that of aluminum and that exhibits an acceptably low level of outgassing in a vacuum.

Particulate Formation from a Copper Oxide-Based Oxygen Carrier in Chemical Looping Combustion for CO2 Capture

EPA Science Inventory

Attrition behavior and particle loss of a copper oxide-based oxygen carrier from a methane chemical looping combustion (CLC) process was investigated in a fluidized bed reactor. The aerodynamic diameters of most elutriated particulates, after passing through a horizontal settling...

Efficacy of copper oxide wire particles against gastrointestinal nematodes in sheep and goats

USDA-ARS?s Scientific Manuscript database

Economic sheep and goat production in the USA is severely limited by gastrointestinal nematode (GIN) parasitism, particularly by Haemonchus contortus, a highly pathogenic blood-feeder. Copper oxide wire particles (COWP) have anti-parasitic properties in the diet of small ruminants, but efficacy of ...

Empirical simulations of materials

NASA Astrophysics Data System (ADS)

Jogireddy, Vasantha

2011-12-01

Molecular dynamics is a specialized discipline of molecular modelling and computer techniques. In this work, first we presented simulation results from a study carried out on silicon nanowires. In the second part of the work, we presented an electrostatic screened coulomb potential developed for studying metal alloys and metal oxides. In particular, we have studied aluminum-copper alloys, aluminum oxides and copper oxides. Parameter optimization for the potential is done using multiobjective optimization algorithms.

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

PubMed

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

2017-09-08

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

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide

PubMed Central

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-01-01

The effect of oxide coating on the activity of a copper-zinc oxide–based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO2 conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides. PMID:28793674

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

PubMed

Urankar, Damijana; Kosmrlj, Janez

2008-01-01

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

Amyloid beta-Cu2+ complexes in both monomeric and fibrillar forms do not generate H2O2 catalytically but quench hydroxyl radicals.

PubMed

Nadal, Rebecca C; Rigby, Stephen E J; Viles, John H

2008-11-04

Oxidative stress plays a key role in Alzheimer's disease (AD). In addition, the abnormally high Cu(2+) ion concentrations present in senile plaques has provoked a substantial interest in the relationship between the amyloid beta peptide (Abeta) found within plaques and redox-active copper ions. There have been a number of studies monitoring reactive oxygen species (ROS) generation by copper and ascorbate that suggest that Abeta acts as a prooxidant producing H2O2. However, others have indicated Abeta acts as an antioxidant, but to date most cell-free studies directly monitoring ROS have not supported this hypothesis. We therefore chose to look again at ROS generation by both monomeric and fibrillar forms of Abeta under aerobic conditions in the presence of Cu(2+) with/without the biological reductant ascorbate in a cell-free system. We used a variety of fluorescence and absorption based assays to monitor the production of ROS, as well as Cu(2+) reduction. In contrast to previous studies, we show here that Abeta does not generate any more ROS than controls of Cu(2+) and ascorbate. Abeta does not silence the redox activity of Cu(2+/+) via chelation, but rather hydroxyl radicals produced as a result of Fenton-Haber Weiss reactions of ascorbate and Cu(2+) rapidly react with Abeta; thus the potentially harmful radicals are quenched. In support of this, chemical modification of the Abeta peptide was examined using (1)H NMR, and specific oxidation sites within the peptide were identified at the histidine and methionine residues. Our studies add significant weight to a modified amyloid cascade hypothesis in which sporadic AD is the result of Abeta being upregulated as a response to oxidative stress. However, our results do not preclude the possibility that Abeta in an oligomeric form may concentrate the redox-active copper at neuronal membranes and so cause lipid peroxidation.

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

PubMed Central

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

2017-01-01

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

Surfactant-free electrodeposition of reduced graphene oxide/copper composite coatings with enhanced wear resistance

NASA Astrophysics Data System (ADS)

Mai, Y. J.; Zhou, M. P.; Ling, H. J.; Chen, F. X.; Lian, W. Q.; Jie, X. H.

2018-03-01

How to uniformly disperse graphene sheets into the electrolyte is one of the main challenges to synthesize graphene enhanced nanocomposites by electrodeposition. A surfactant-free colloidal solution comprised of copper (II)-ethylene diamine tetra acetic acid ([CuIIEDTA]2-) complexes and graphene oxide (GO) sheets is proposed to electrodeposit reduced graphene oxide/copper (RGO/Cu) composite coatings. Anionic [CuIIEDTA]2- complexes stably coexist with negatively charged GO sheets due to the electrostatic repulsion between them, facilitating the electrochemical reduction and uniform dispersion of GO sheets into the copper matrix. The RGO/Cu composite coatings are well characterized by XRD, Raman, SEM and XPS. Their tribological behavior as a function of RGO content in composite coatings and normal loads are investigated. Also the chemical composition and topography of the wear tracks for the composite coatings are analyzed to deduce the lubricating and anti-wear mechanism of RGO/Cu composite coatings.

Decomposition of poly(amide-imide) film enameled on solid copper wire using atmospheric pressure non-equilibrium plasma.

PubMed

Sugiyama, Kazuo; Suzuki, Katsunori; Kuwasima, Shusuke; Aoki, Yosuke; Yajima, Tatsuhiko

2009-01-01

The decomposition of a poly(amide-imide) thin film coated on a solid copper wire was attempted using atmospheric pressure non-equilibrium plasma. The plasma was produced by applying microwave power to an electrically conductive material in a gas mixture of argon, oxygen, and hydrogen. The poly(amide-imide) thin film was easily decomposed by argon-oxygen mixed gas plasma and an oxidized copper surface was obtained. The reduction of the oxidized surface with argon-hydrogen mixed gas plasma rapidly yielded a metallic copper surface. A continuous plasma heat-treatment process using a combination of both the argon-oxygen plasma and argon-hydrogen plasma was found to be suitable for the decomposition of the poly(amide-imide) thin film coated on the solid copper wire.

Graphene oxide alleviates the ecotoxicity of copper on the freshwater microalga Scenedesmus obliquus.

PubMed

Hu, Changwei; Hu, Naitao; Li, Xiuling; Zhao, Yongjun

2016-10-01

The extensive industrial application of graphene oxide (GO), has increased its exposure risk to various aquatic organisms and its potential to affect the toxicity of other environmental pollutants. In this study, we investigated the combined toxicity of GO and copper on the freshwater microalga Scenedesmus obliquus, using the MIXTOX model. The effects of low concentration (1mg/L) exposure to GO were investigated with environmentally relevant concentrations of copper by using a 12-d subacute toxicity test, with pre- and post-GO treatment. Results showed that there were significant antagonistic effects between GO and copper on S. obliquus, and GO was found to reduce ecotoxicity of copper even at low and environmentally relevant concentrations (1mg/L). Copyright © 2016 Elsevier Inc. All rights reserved.

Change spectroscopic studies and optimization electrical properties of PVP/PEO doped copper phthalocyanines

NASA Astrophysics Data System (ADS)

Ragab, H. M.; Ahmad, F.; Radwan, Sh. N.

2016-12-01

Composite films of polyvinyl pyrrolidone and Polyethylene oxide (PVP/PEO) blend doped with 1, 4 and 12 wt% of copper Phthalocyanines (CuPc) were prepared by casting method. The samples were studied using different techniques. The X-ray (XRD) revealed average crystallite size and X-ray intensity decrease at 1 CuPc %; this implies to an increase on the degree of amorphousity, then increase at CuPc >1%. The change in both the intensity and position of some absorption peaks of the blend with CuPc content were observed in Fourier transform infrared (FTIR) spectroscopy suggest the complexation of polymer blend. The UV-Vis spectroscopy revealed that the optical band gap decreases as well as band tail width increases with increasing CuPc concentration. It may be reflect the role of CuPc in modifying the electronic structure of the polymeric matrix. The charge carrier concentration is responsible for conductivity improvement in electrolytes rather than the mobility.

The partitioning of copper among selected phases of geologic media of two porphyry copper districts, Puerto Rico

USGS Publications Warehouse

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

1981-01-01

In experiments designed to determine the manner in which copper is partitioned among selected phases that constitute geologic media, we have applied the five-step sequential extraction procedure of Chao and Theobald to the analysis of drill core, soils, and stream sediments of the Rio Vivi and Rio Tanama porphyry copper districts of Puerto Rico. The extraction procedure affords a convenient means of determining the trace-metal content of the following fractions: (1) Mn oxides and "reactive" Fe oxides; (2) "amorphous" Fe oxides; (3) "crystalline" Fe oxides; (4) sulfides and magnetite; and (5) silicates. An additional extraction between steps (1) and (2) was performed to determine organic-related copper in stream sediments. The experimental results indicate that apportionment of copper among phases constituting geologic media is a function of geochemical environment. Distinctive partitioning patterns were derived from the analysis of drill core from each of three geochemical zones: (a) the supergene zone of oxidation; (b) the supergene zone of enrichment; and (c) the hypogene zone; and similarly, from the analysis of; (d) soils on a weakly leached capping; (e) soils on a strongly leached capping; and (f) active stream sediment. The experimental results also show that geochemical contrasts (anomaly-to-background ratios) vary widely among the five fractions of each sampling medium investigated, and that at least one fraction of each medium provides substantially stronger contrast than does the bulk medium. Fraction (1) provides optimal contrast for stream sediments of the district; fraction (2) provides optimal contrast for soils on a weakly leached capping; fraction (3) provides optimal contrast for soils on a strongly leached capping. Selective extraction procedures appear to have important applications to the orientation and interpretive stages of geochemical exploration. Further investigation and testing of a similar nature are recommended. ?? 1981.

Copper supplementation amplifies the anti-tumor effect of curcumin in oral cancer cells.

PubMed

Lee, Hui-Mei; Patel, Vyomesh; Shyur, Lie-Fen; Lee, Wai-Leng

2016-11-15

Oral cancer is the sixth most common cancer worldwide and 90% of oral malignancies are caused by oral squamous cell carcinoma (OSCC). Curcumin, a phytocompound derived from turmeric (Curcuma longa) was observed to have anti-cancer activity which can be developed as an alternative treatment option for OSCC. However, OSCC cells with various clinical-pathological features respond differentially to curcumin treatment. Intracellular copper levels have been reported to correlate with tumor pathogenesis and affect the sensitivity of cancer cells to cytotoxic chemotherapy. We hypothesized that intracellular copper levels may affect the sensitivity of oral cancer cells to curcumin. We analysed the correlation between intracellular copper levels and response to curcumin treatment in a panel of OSCC cell lines derived from oral cancer patients. Exogenous copper was supplemented in curcumin insensitive cell lines to observe the effect of copper on curcumin-mediated inhibition of cell viability and migration, as well as induction of oxidative stress and apoptosis. Protein markers of cell migration and oxidative stress were also analysed using Western blotting. Concentrations of curcumin which inhibited 50% OSCC cell viability (IC 50 ) was reduced up to 5 times in the presence of 250 µM copper. Increased copper level in curcumin-treated OSCC cells was accompanied by the induction of intracellular ROS and increased level of Nrf2 which regulates oxidative stress responses in cells. Supplemental copper also inhibited migration of curcumin-treated cells with enhanced level of E-cadherin and decreased vimentin, indications of suppressed epithelial-mesenchymal transition. Early apoptosis was observed in combined treatment but not in treatment with curcumin or copper alone. Supplement of copper significantly enhanced the inhibitory effect of curcumin treatment on migration and viability of oral cancer cells. Together, these findings provide molecular insight into the role of copper in overcoming insensitivity of oral cancer cells to curcumin treatment, suggesting a new strategy for cancer therapy. Copyright © 2016 Elsevier GmbH. All rights reserved.

Copper-catalyzed aerobic oxidative synthesis of α-ketoamides from methyl ketones, amines and NIS at room temperature.

PubMed

Zhang, Juan; Wei, Ying; Lin, Shaoxia; Liang, Fushun; Liu, Pengjun

2012-12-14

A simple, efficient and practical copper-catalyzed aerobic oxidative synthesis of α-ketoamides from aryl methyl ketones, aliphatic amines and N-iodosuccinimide (NIS) has been developed. The one-pot reaction may proceed smoothly at room temperature in the open air. The possible mechanism for the formation of α-ketoamides was proposed. Molecular oxygen in air functions as both an oxidant and an oxygen source.

Investigation into Spectroscopic Techniques for Thermal Barrier Coating Spall Detection

NASA Technical Reports Server (NTRS)

deGroot, Wim; Opila, Beth

2001-01-01

Spectroscopic methods are proposed for detection of thermal barrier coating (TBC) spallation from engine hot zone components. These methods include absorption and emission of airborne marker species originally embedded in the TBC bond coat. In this study, candidate marker materials for this application were evaluated. Thermochemical analysis of candidate marker materials combined with additional constraints such as toxicity and uniqueness to engine environment, provided a short list of four potential species: platinum, copper oxide, zinc oxide. and indium. The melting point of indium was considered to be too low for serious consideration. The other three candidate marker materials, platinum, copper oxide, and zinc oxide were placed in a high temperature furnace and emission and absorption properties were measured over a temperature range from 800-1400 C and a spectral range from 250 to 18000 nm. Platinum did not provide the desired response, likely due to the low vapor Pressure of the metallic species and the low absorption of the oxide species. It was also found, however. that platinum caused a broadening of the carbon dioxide absorption at 4300 nm. The nature of this effect is not known. Absorption and emission caused by sodium and potassium impurities in the platinum were found in the platinum tests. Zinc oxide did not provide the desired response, again, most likely due to the low vapor pressure of the metallic species and the low absorption of the oxide species. Copper oxide generated two strongly temperature dependent absorption peaks at 324.8 and 327.4 nm. The melting point of copper oxide was determined to be too low for serious consideration as marker material.

Examination of commercially available copper oxide wire particles in combination with albendazole for control of gastrointestinal nematodes in lambs

USDA-ARS?s Scientific Manuscript database

Alternatives to synthetic anthelmintics remain critical due to the prevalence of anthelmintic resistance. The objective of the experiment was to determine the efficacy of copper oxide wire particles (COWP) from three commercial sources to control Haemonchus contortus in lambs. Naturally infected Ka...

Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

PubMed

Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

2012-06-27

Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

Evolution of the Copper Surface in the Course of Oxidation by CCl4-L (L=THF, Dmf, Dmso): Scanning Probe Microscope Study

NASA Astrophysics Data System (ADS)

Panteleev, S. V.; Maslennikov, S. V.; Ignatov, S. K.; Spirina, I. V.; Kruglova, M. V.; Gribkov, B. A.; Vdovichev, S. N.

2013-04-01

The evolution of compact surface of the 100 nm copper film deposited on the glass-ceramics doped with vanadium coating in the course of the oxidation by the CCl4-L (L = dimethylformamide (DMF), tetrahydrofuran (THF), dimethylsulfoxide (DMSO), CCl4 concentration ≈ 1 mol/L) was studied by atomic force microscopy (AFM) in contact mode. The dynamics of active centers formation and destruction was investigated in the course of the oxidation process. The metallic sample dissolution rate was estimated as a function of the coordinating solvent nature. The development of the metal surface oxidation was established to lead to a significant increase of surface roughness. This phenomenon can be explained by the fact that different parts of the surface react at different rates. Further course of the reaction leads to a significant decrease of the surface roughness of copper films. The amount of the metal reacted has an almost linear dependence on the reaction time. AFM scans indicate that there is the same mechanism of the reaction between copper and carbon tetrachloride for all solvents.

Copper-catalyzed Huisgen and oxidative Huisgen coupling reactions controlled by polysiloxane-supported amines (AFPs) for the divergent synthesis of triazoles and bistriazoles.

PubMed

Zheng, Zhan-Jiang; Ye, Fei; Zheng, Long-Sheng; Yang, Ke-Fang; Lai, Guo-Qiao; Xu, Li-Wen

2012-10-29

An interesting example of a divergent catalysis with a copper(I) and amine-functional macromolecular polysiloxanes system was successfully presented in click chemistry. In this manuscript, we demonstrate the remarkable ability of the secondary amine-functional polysiloxane to induce oxidative coupling in the copper-mediated Huisgen reactions of azides and alkynes, thereby achieving good yields and selectivities. The click reactions mediated by a polysiloxane-supported secondary amine allow the preparation of novel heterocyclic compounds, that is, bistriazoles. Comparably, it is also surprising that the use of a diamine-functional polysiloxane as ligand led to a classic Huisgen [3+2] cycloaddition in excellent yields. From the results of the present amine-functional polysiloxanes-controlled Huisgen reaction or oxidative Huisgen coupling reaction to divergent products and the proposed mechanism, we suggested that the mononuclear bistriazole-copper complex stabilized and dispersed by the secondary amine-functional polysiloxane was beneficial to prevalent the way to oxidative coupling. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

Gold coated copper artifacts from the Royal Tombs of Sipán (Huaca Rajada, Perù): manufacturing techniques and corrosion phenomena

NASA Astrophysics Data System (ADS)

Ingo, Gabriel M.; Bustamante, Angel D.; Alva, Walter; Angelini, Emma; Cesareo, Roberto; Gigante, Giovanni E.; Zambrano, Sandra Del Pilar A.; Riccucci, Cristina; Di Carlo, Gabriella; Parisi, Erica I.; Faraldi, Federica; Chero, Luis; Fabian, Julio S.

2013-12-01

Twenty five years ago, close to the northern Peruvian town of Lambayeque (Huaca Rajada) beneath two large and eroded pyramids, built of adobe mud bricks, Professor Alva discovered the world-famous unlooted pre-Columbian burial chambers of the Royal Tombs of Sipan. The tombs contained a large amount of objects of exceptional artistic and historical value including the greatest intact number of gold and silver artefacts in the Americas to be considered one of the most important archaeological discoveries of the last century. Some copper based objects coated with thin layers of gold have been studied by means of the combined use of analytical techniques such as optical microscopy (OM), scanning electron microscopy coupled with energy dispersive X-ray micro-analysis (SEM-EDS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) in order to identify the chemical composition and the manufacturing processes of the gold layer as well as the corrosion products formed during the long-term burial. The micro-chemical and structural results give useful information about the manufacturing techniques used by the Moche metalsmiths to modify the surface chemical composition of the coated artefacts likely based on the depletion gilding process carried out by oxidising the surface copper containing the noble metal and etching away the copper oxides. Furthermore, the results reveal that the main degradation agent is the ubiquitous chlorine and that copper has been almost completely transformed during the burial into mineral species giving rise to the formation of stratified structures constituted by different mineral phases such as cuprous oxide (Cu2O) and copper carbonates [azurite (Cu3(CO3)2(OH)2 and malachite (CuCO3Cu(OH)2)] as well as dangerous chlorine-based compounds such as nantokite (CuCl) and atacamite (Cu2(OH)3Cl) polymorphs. These information evidence the strict interaction of the alloying elements with the soil components as well as the occurrence of the copper cyclic corrosion as post-burial degradation phenomenon. The present study confirms that the combined use of micro-chemical and micro-structural investigation techniques such as SEM-EDS, XPS, XRD, and OM can be successfully used to investigate the technological manufacturing processes of the ancient coated artefacts and to achieve information about degradation agents and mechanisms useful to define tailored conservation strategies possibly including new, more reliable, and safer materials.

Reduction of healthcare-associated infections in a long-term care brain injury ward by replacing regular linens with biocidal copper oxide impregnated linens.

PubMed

Lazary, A; Weinberg, I; Vatine, J-J; Jefidoff, A; Bardenstein, R; Borkow, G; Ohana, N

2014-07-01

Contaminated textiles in hospitals contribute to endogenous, indirect-contact, and aerosol transmission of nosocomial related pathogens. Copper oxide impregnated linens have wide-spectrum antimicrobial, antifungal, and antiviral properties. Our aim was to determine if replacing non-biocidal linens with biocidal copper oxide impregnated linens would reduce the rates of healthcare-associated infections (HAI) in a long-term care ward. We compared the rates of HAI in two analogous patient cohorts in a head injury care ward over two 6-month parallel periods before (period A) and after (period B) replacing all the regular non-biocidal linens and personnel uniforms with copper oxide impregnated biocidal products. During period B, in comparison to period A, there was a 24% reduction in the HAI per 1000 hospitalization-days (p<0.05), a 47% reduction in the number of fever days (>38.5°C) per 1000 hospitalization-days (p<0.01), and a 32.8% reduction in total number of days of antibiotic administration per 1000 hospitalization-days (p<0.0001). Accordingly there was saving of approximately 27% in costs of antibiotics, HAI-related treatments, X-rays, disposables, labor, and laundry, expenses during period B. The use of biocidal copper oxide impregnated textiles in a long-term care ward may significantly reduce HAI, fever, antibiotic consumption, and related treatment costs. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

High specific heat superconducting composite

DOEpatents

Steyert, Jr., William A.

1979-01-01

A composite superconductor formed from a high specific heat ceramic such as gadolinium oxide or gadolinium-aluminum oxide and a conventional metal conductor such as copper or aluminum which are insolubly mixed together to provide adiabatic stability in a superconducting mode of operation. The addition of a few percent of insoluble gadolinium-aluminum oxide powder or gadolinium oxide powder to copper, increases the measured specific heat of the composite by one to two orders of magnitude below the 5.degree. K. level while maintaining the high thermal and electrical conductivity of the conventional metal conductor.

Synthesis of highly phase pure BSCCO superconductors

DOEpatents

Dorris, S.E.; Poeppel, R.B.; Prorok, B.C.; Lanagan, M.T.; Maroni, V.A.

1995-11-21

An article and method of manufacture (Bi, Pb)-Sr-Ca-Cu-O superconductor are disclosed. The superconductor is manufactured by preparing a first powdered mixture of bismuth oxide, lead oxide, strontium carbonate, calcium carbonate and copper oxide. A second powdered mixture is then prepared of strontium carbonate, calcium carbonate and copper oxide. The mixtures are calcined separately with the two mixtures then combined. The resulting combined mixture is then subjected to a powder in tube deformation and thermal processing to produce a substantially phase pure (Bi, Pb)-Sr-Ca-Cu-O superconductor. 5 figs.

Synthesis of highly phase pure BSCCO superconductors

DOEpatents

Dorris, Stephen E.; Poeppel, Roger B.; Prorok, Barton C.; Lanagan, Michael T.; Maroni, Victor A.

1995-01-01

An article and method of manufacture of (Bi, Pb)-Sr-Ca-Cu-O superconductor. The superconductor is manufactured by preparing a first powdered mixture of bismuth oxide, lead oxide, strontium carbonate, calcium carbonate and copper oxide. A second powdered mixture is then prepared of strontium carbonate, calcium carbonate and copper oxide. The mixtures are calcined separately with the two mixtures then combined. The resulting combined mixture is then subjected to a powder in tube deformation and thermal processing to produce a substantially phase pure (Bi, Pb)-Sr-Ca-Cu-O superconductor.

Synthesis of highly phase pure (Bi, Pb)-Sr-Ca-Cu-O superconductor

DOEpatents

Dorris, Stephen E.; Poeppel, Roger B.; Prorok, Barton C.; Lanagan, Michael T.; Maroni, Victor A.

1994-01-01

An article and method of manufacture of (Bi,Pb)-Sr-Ca-Cu-O superconductor. The superconductor is manufactured by preparing a first powdered mixture of bismuth oxide, lead oxide, strontium carbonate, calcium carbonate and copper oxide. A second powdered mixture is then prepared of strontium carbonate, calcium carbonate and copper oxide. The mixtures are calcined separately with the two mixtures then combined. The resulting combined mixture is then subjected to a powder in tube deformation and thermal processing to produce a substantially phase pure (Bi,Pb)-Sr-Ca-Cu-O superconductor.

Ultra-deep oxidation and exotic copper formation at the late pliocene boyongan and bayugo porphyry copper-gold deposits, surigao, philippines: Geology, mineralogy, paleoaltimetry, and their implications for Geologic, physiographic, and tectonic controls

USGS Publications Warehouse

Braxton, D.P.; Cooke, D.R.; Ignacio, A.M.; Rye, R.O.; Waters, P.J.

2009-01-01

The Boyongan and Bayugo porphyry copper-gold deposits are part of an emerging belt of intrusion-centered gold-rich deposits in the Surigao district of northeast Mindanao, Philippines. Exhumation and weathering of these Late Pliocene-age deposits has led to the development of the world's deepest known porphyry oxidation profile at Boyongan (600 m), and yet only a modest (30-70 m) oxidation profile at adjacent Bayugo. Debris flows, volcanic rocks, and fluviolacustrine sediments accumulating in the actively extending Mainit graben subsequently covered the deposits and preserved the supergene profiles. At Boyongan and Bayugo, there is a vertical transition from shallower supergene copper oxide minerals (malachite + azurite + cuprite) to deeper sulfide-stable assemblages (chalcocite ?? hypogene sulfides). This transition provides a time-integrated proxy for the position of the water table at the base of the saturated zone during supergene oxidation. Contours of the elevation of the paleopotentiometric surface based on this min- eralogical transition show that the thickest portions of the unsaturated zone coincided with a silt-sand matrix diatreme breccia complex at Boyongan. Within the breccia complex, the thickness of the unsaturated zone approached 600 in, whereas outside the breccia complex (e.g., at Bayugo), the thickness averaged 50 m. Contours of the paleopotentiometric surface suggest that during weathering, groundwater flowed into the breccia complex from the north, south, and east, and exited along a high permeability zone to the west. The high relief (>550 m) on the elevation of the paleopotentiometric surface is consistent with an environment of high topographic relief, and the outflow zone to the west of the breccia complex probably reflects proximity to a steep scarp intersecting the western breccia complex margin. Stable isotope paleoaltimetry has enabled estimation of the elevation of the land surface, which further constrains the physiographic setting during supergene oxidation. Isotopic measurements of oxygen in supergene kaolinite from Boyongan suggest that local paleometeoric water involved in weathering had a ??180 composition of approximately -5.7 per mil. At the latitude of the southern Philippines, this value corresponds to Pleistocene rain water condensing at elevations between 750 and 1,050 m above contemporary sea level, providing a maximum estimate for the surface elevation during weathering of the porphyry systems. Physiographic reconstuctions suggest that the deep oxidation profile at Boyongan formed in an environment of high topographic relief immediately east of a prominent (>550 m) escarpment. The high permeability contrast between the breccia complex and the surrounding wall rocks, coupled with the proximity of the breccia complex to the escarpment, led to a depressed groundwater table and a vertically extensive unsaturated zone in the immediate vicinity of Boyongan. This thick vadose zone and the low hypogene pyrite/copper sulfide ratios (0.6) at Boyongan promoted in situ oxidation of copper sulfides with only modest (<200 m) supergene remobilization of copper. In contrast, higher hypogene pyrite/chalcopyrite ratios (2.3) at Bayugo led to greater acid production during weathering and more complete leaching of copper above the base of oxidation. This process promoted significant (600 m) lateral dispersion of copper down the paleohydraulic gradient into the diatreme breccia comple, ultimately leading to the formation of an exotic copper deposit. ?? 2009 Society of Economices Geologists, Inc.

Enhanced activity and stability of copper oxide/γ-alumina catalyst in catalytic wet-air oxidation: Critical roles of cerium incorporation

NASA Astrophysics Data System (ADS)

Zhang, Yongli; Zhou, Yanbo; Peng, Chao; Shi, Junjun; Wang, Qingyu; He, Lingfeng; Shi, Liang

2018-04-01

By successive impregnation method, the Ce-modified Cu-O/γ-Al2O3 catalyst was prepared and characterized using nitrogen adsorption-desorption, scanning electron microscopy energy dispersive X-ray analysis (SEM-EDS), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, and H2-Temperature programming reduction (H2-TPR). In catalytic wet-air oxidation (CWAO) process for the printing and dyeing wastewater (PDW), the effects of Ce addition on performance, mechanism and kinetics of the catalyst were investigated. The Ce addition increases the Brunauer-Emmett-Teller (BET) surface area and pore volume of the catalyst and makes the active components uniformly distributed on the catalyst surface. Formation of a stable CuAl2O4 solid solution by anchoring Cu onto the γ-Al2O3 crystal lattice leads to a significant decrease in metal leaching of the Ce-modified catalyst. The proportion of lattice oxygen in the catalyst substantially increases and the apparent activation energy of Cu-O/γ-Al2O3 catalyst decreases owing to Ce addition. Therefore, the catalytic activity and stability of the Ce-modified catalyst are considerably improved. The scavengers experiments identify the active species existed in the CWAO reaction system, with the order of reactivity: h+ > O2•- > H2O2 > HO•. This novel Cu-Ce-O/γ-Al2O3 catalyst has great potential in applications for treatment of concentrated organic wastewater due to its superior catalytic activity and improved stability.

Oxidation Behavior of GRCop-84 Copper Alloy Assessed

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, Linus U.

2002-01-01

NASA's goal of safe, affordable space transportation calls for increased reliability and lifetimes of launch vehicles, and significant reductions of launch costs. The areas targeted for enhanced performance in the next generation of reusable launch vehicles include combustion chambers and nozzle ramps; therefore, the search is on for suitable liner materials for these components. GRCop-84 (Cu-8Cr-4Nb), an advanced copper alloy developed at the NASA Glenn Research Center in conjunction with Case Western Reserve University, is a candidate. The current liner of the Space Shuttle Main Engine is another copper alloy, NARloy-Z (Cu-3Ag-0.1Zr). It provides a benchmark against which to compare the properties of candidate successors. The thermomechanical properties of GRCop-84 have been shown to be superior, and its physical properties comparable, to those of NARloy-Z. However, environmental durability issues control longevity in this application: because copper oxide scales are not highly protective, most copper alloys are quickly consumed in oxygen environments at elevated temperatures. In consequence, NARloy-Z and most other copper alloys are prone to blanching, a degradation process that occurs through cycles of oxidation-reduction as the oxide is repeatedly formed and removed because of microscale fluctuations in the oxygen-hydrogen fuel systems of rocket engines. The Space Shuttle Main Engine lining typically degraded by blanching-induced hot spots that lead to surface roughening, pore formation, and coolant leakage. Therefore, resistance to oxidation and blanching are key requirements for second-generation reusable launch vehicle liners. The rocket engine ambient includes H2 (fuel) and H2O (combustion product) and is, hence, under reduced oxygen partial pressures. Accordingly, our studies were expanded to include oxygen partial pressures as low as 322 parts per million (ppm) at the temperatures likely to be experienced in service. A comparison of 10-hr weight gains of GRCop-84, NARloy-Z, and pure copper in 0.032, 2.2, and 100 percent oxygen from 550 to 750 C is shown. In 2.2 vol% and higher oxygen content, GRCop-84 oxidation was slower than that of NARloy-Z or Cu, but that advantage was lost or diminished in 322-ppm O2. Over longer (50-hr) exposures in 1.0 atm O2, however, the advantage of GRCop-84 increased significantly, its oxidation rate becoming approximately 10 times slower than those of Cu and NARloy-Z from 500 to 700 C. Weight gains were moderate and the kinetics parabolic for all three materials in 2.2 vol% and higher oxygen content; however, in 322-ppm O2, the scales were nonprotective below about 650 C, as reflected in linear kinetics and large weight gains. The superior oxidation resistance of GRCop-84 is likely related to the kinetics of extra oxygen consumption to form the additional oxides of Cr and Nb detected beneath the GRCop-84 oxide layer. While we continue to evaluate the blanching resistance of GRCop-84 in other tests, these oxidation results indicate that GRCop-84 is suitable as a reusable launch vehicle liner, and in applications where it is desired to use a copper alloy but without the risk of oxidative failure. Three bar charts comparing overall specific weight gains by each of the three materials studied. The top chart is for oxidation in 1.0 atm of oxygen, the middle is for 2.2% oxygen (balance argon), and the bottom is for 0.0322% oxygen. GRCop-84 outperforms the other two materials, showing the least weight gain in nearly all cases.

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

NASA Astrophysics Data System (ADS)

Rhinow, Daniel; Hampp, Norbert A.

2012-06-01

Self-assembled monolayers (SAMs) of alkanethiols are major building blocks for nanotechnology. SAMs provide a functional interface between electrodes and biomolecules, which makes them attractive for biochip fabrication. Although gold has emerged as a standard, copper has several advantages, such as compatibility with semiconductors. However, as copper is easily oxidized in air, patterning SAMs on copper is a challenging task. In this work we demonstrate that submerged laser ablation (SLAB) is well-suited for this purpose, as thiols are exchanged in-situ, avoiding air exposition. Using different types of ω-substituted alkanethiols we show that alkanethiol SAMs on copper surfaces can be patterned using SLAB. The resulting patterns were analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Both methods indicate that the intense laser beam promotes the exchange of thiols at the copper surface. Furthermore, we present a procedure for the production of free-standing copper nanomembranes, oxidation-protected by alkanethiol SAMs. Incubation of copper-coated mica in alkanethiol solutions leads to SAM formation on both surfaces of the copper film due to intercalation of the organic molecules. Corrosion-protected copper nanomembranes were floated onto water, transferred to electron microscopy grids, and subsequently analyzed by electron energy loss spectroscopy (EELS).

Synergy of iron and copper oxides in the catalytic formation of PCDD/Fs from 2-monochlorophenol.

PubMed

Potter, Phillip M; Guan, Xia; Lomnicki, Slawomir M

2018-07-01

Transition metal oxides present in waste incineration systems have the ability to catalyze the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through surface reactions involving organic dioxin precursors. However, studies have concentrated on the catalytic effects of individual transition metal oxides, while the complex elemental composition of fly ash introduces the possibility of synergistic or inhibiting effects between multiple, catalytically active components. In this study, we have tested fly ash surrogates containing different ratios (by weight) of iron (III) oxide and copper (II) oxide. Such Fe 2 O 3 /CuO mixed-oxide surrogates (in the Fe:Cu ratio of 3.5, 0.9 and 0.2 ) were used to study the cooperative effects between two transition metals that are present in high concentrations in most combustion systems and are known to individually catalyze the formation of PCDD/Fs. The presence of both iron and copper oxides increased the oxidative power of the fly ash surrogates in oxygen rich conditions and led to extremely high PCDD/F yields under pyrolytic conditions (up to >5% yield) from 2-monochlorophenol precursor. PCDD/F congener profiles from the mixed oxide samples are similar to results obtained from only CuO, however the total PCDD/F yield increases with increasing Fe 2 O 3 content. Careful analysis of the reaction products and changes to the oxidation states of active metals indicate the CuO surface sites are centers for reaction while the Fe 2 O 3 is affecting the bonds in CuO and increasing the ability of copper centers to form surface-bound radicals that are precursors to PCDD/Fs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Cu(II)-catalyzed oxidation of dopamine in aqueous solutions: mechanism and kinetics.

PubMed

Pham, A Ninh; Waite, T David

2014-08-01

Spontaneous oxidation of dopamine (DA) and the resultant formation of free radical species within dopamine neurons of the substantia nigra (SN) is thought to bestow a considerable oxidative load upon these neurons and may contribute to their vulnerability to degeneration in Parkinson's disease (PD). An understanding of DA oxidation under physiological conditions is thus critical to understanding the relatively selective vulnerability of these dopaminergic neurons in PD and may support the development of novel neuro-protective approaches for this disorder. In this study, the oxidation of dopamine (0.2-10μM) was investigated both in the absence and the presence of copper (0.01-0.4μM), a redox active metal that is present at considerable concentrations in the SN, over a range of background chloride concentrations (0.01-0.7M), different oxygen concentrations and at physiological pH7.4. DA was observed to oxidize extremely slowly in the absence of copper and at moderate rates only in the presence of copper but without chloride. The oxidation of DA however was significantly enhanced in the presence of both copper and chloride with the rate of DA oxidation greatest at intermediate chloride concentrations (0.05-0.2M). The variability of the catalytic effect of Cu(II) on DA oxidation at different chloride concentrations can be explained and successfully modeled by appropriate consideration of the reaction of Cu(II) species with DA and the conversion of Cu(I) to Cu(II) through oxygenation. This model suggests that the speciation of Cu(II) and Cu(I) is critically important to the kinetics of DA oxidation and thus the vulnerability to degradation of dopaminergic neuron in the brain milieu. Copyright © 2014 Elsevier Inc. All rights reserved.

Investigation of Industrial Polyurethane Foams Modified with Antimicrobial Copper Nanoparticles

PubMed Central

Sportelli, Maria Chiara; Picca, Rosaria Anna; Ronco, Roberto; Bonerba, Elisabetta; Tantillo, Giuseppina; Pollini, Mauro; Sannino, Alessandro; Valentini, Antonio; Cataldi, Tommaso R.I.; Cioffi, Nicola

2016-01-01

Antimicrobial copper nanoparticles (CuNPs) were electrosynthetized and applied to the controlled impregnation of industrial polyurethane foams used as padding in the textile production or as filters for air conditioning systems. CuNP-modified materials were investigated and characterized morphologically and spectroscopically, by means of Transmission Electron Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS). The release of copper ions in solution was studied by Electro-Thermal Atomic Absorption Spectroscopy (ETAAS). Finally, the antimicrobial activity of freshly prepared, as well as aged samples—stored for two months—was demonstrated towards different target microorganisms. PMID:28773665

Exploring monovalent copper compounds with oxygen and hydrogen

PubMed Central

Korzhavyi, Pavel A.; Soroka, Inna L.; Isaev, Eyvaz I.; Lilja, Christina; Johansson, Börje

2012-01-01

New important applications of copper metal, e.g., in the areas of hydrogen production, fuel cell operation, and spent nuclear fuel disposal, require accurate knowledge of the physical and chemical properties of stable and metastable copper compounds. Among the copper(I) compounds with oxygen and hydrogen, cuprous oxide Cu2O is the only one stable and the best studied. Other such compounds are less known (CuH) or totally unknown (CuOH) due to their instability relative to the oxide. Here we combine quantum-mechanical calculations with experimental studies to search for possible compounds of monovalent copper. Cuprous hydride (CuH) and cuprous hydroxide (CuOH) are proved to exist in solid form. We establish the chemical and physical properties of these compounds, thereby filling the existing gaps in our understanding of hydrogen- and oxygen-related phenomena in Cu metal. PMID:22219370

Adsorption of Cu2+ to biomass ash and its modified product.

PubMed

Xu, Lei; Cui, Hongbiao; Zheng, Xuebo; Liang, Jiani; Xing, Xiangyu; Yao, Lunguang; Chen, Zhaojin; Zhou, Jing

2017-04-01

Ash produced by biomass power plants has great potential for the removal of heavy metal ions from aqueous solution. The pollution of toxic heavy metals to water is a worldwide environmental problem. Discharges containing copper, in particular, are strictly controlled because the excessive copper can cause serious harm to the environment and human health. This work aims to investigate the adsorption characteristics of copper ions in aqueous solution by biomass ash and the modified products, and to evaluate their potential application in water pollution control. The biomass ash was modified with a mesoporous siliceous material and functionalized with 3-aminopropyltriethoxysilane. The surface properties of the biomass ash and the new matrix were studied to evaluate their adsorption property for Cu 2+ ions at different pHs, initial metal concentrations and the thermodynamic and kinetic were studied. The chemical and morphological properties of this modified material are analyzed; the specific surface area of the modified biomass ash was nine times that of the initial ash. Both of the two materials showed a strong affinity for Cu 2+ , and the Langmuir model could best represent the adsorption characteristics of Cu 2+ on the two kinds of materials. The adsorption capacity of copper on the material increased with the increase of pH and pH 6 was the optimum pH. Thermodynamic analysis results showed that the adsorption of Cu 2+ was spontaneous and endothermic in nature. The adsorptions of Cu 2+ onto the modified biomass ash followed pseudo-second-order kinetics.

Large-scale fabrication of single crystalline tin nanowire arrays

NASA Astrophysics Data System (ADS)

Luo, Bin; Yang, Dachi; Liang, Minghui; Zhi, Linjie

2010-09-01

Large-scale single crystalline tin nanowire arrays with preferred lattice orientation along the [100] direction were fabricated in porous anodic aluminium oxide (AAO) membranes by the electrodeposition method using copper nanorod as a second electrode.Large-scale single crystalline tin nanowire arrays with preferred lattice orientation along the [100] direction were fabricated in porous anodic aluminium oxide (AAO) membranes by the electrodeposition method using copper nanorod as a second electrode. Electronic supplementary information (ESI) available: Experimental details and the information for single crystalline copper nanorods. See DOI: 10.1039/c0nr00206b

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

PubMed

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

2011-07-01

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

Calcium phosphate coatings modified with zinc- or copper- incorporation on Ti-40Nb alloy

NASA Astrophysics Data System (ADS)

Komarova, E. G.; Sedelnikova, M. B.; Sharkeev, Yu P.; Kazakbaeva, A. A.; Glukhov, I. A.; Khimich, M. A.

2017-05-01

The influence of the microarc oxidation parameters and electrolyte composition on the structure, properties and composition of CaP coatings modified with Zn- or Cu- incorporation on the Ti-40mas.%Nb (Ti-40Nb) alloy was investigated. The linear growth of thickness, roughness, and size of structural elements with process voltage increasing has been revealed. It was shown that the CaP coatings have the low contact angles with liquids and, consequently, high free surface energy. This indicates a high hydrophilicity of the coatings. X-ray diffraction analysis showed that the coatings have X-ray amorphous structure. The increase of the process voltage leads to the formation of such crystalline phases as CaHPO4 and β-Ca2P2O7 in the coatings. The maximum Ca/P atomic ratio was equal to 0.4, and Zn or Cu contents was equal to 0.3 or 0.2 at.%, respectively.

Tumor Lysing Genetically Engineered T Cells Loaded with Multi-Modal Imaging Agents

NASA Astrophysics Data System (ADS)

Bhatnagar, Parijat; Alauddin, Mian; Bankson, James A.; Kirui, Dickson; Seifi, Payam; Huls, Helen; Lee, Dean A.; Babakhani, Aydin; Ferrari, Mauro; Li, King C.; Cooper, Laurence J. N.

2014-03-01

Genetically-modified T cells expressing chimeric antigen receptors (CAR) exert anti-tumor effect by identifying tumor-associated antigen (TAA), independent of major histocompatibility complex. For maximal efficacy and safety of adoptively transferred cells, imaging their biodistribution is critical. This will determine if cells home to the tumor and assist in moderating cell dose. Here, T cells are modified to express CAR. An efficient, non-toxic process with potential for cGMP compliance is developed for loading high cell number with multi-modal (PET-MRI) contrast agents (Super Paramagnetic Iron Oxide Nanoparticles - Copper-64; SPION-64Cu). This can now be potentially used for 64Cu-based whole-body PET to detect T cell accumulation region with high-sensitivity, followed by SPION-based MRI of these regions for high-resolution anatomically correlated images of T cells. CD19-specific-CAR+SPIONpos T cells effectively target in vitro CD19+ lymphoma.

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

NASA Astrophysics Data System (ADS)

Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

2018-05-01

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

Electrodeposition of reduced graphene oxide with chitosan based on the coordination deposition method

PubMed Central

Liu, Mingyang; Qin, Chaoran; Zhang, Zheng; Ma, Shuai; Cai, Xiuru; Li, Xueqian

2018-01-01

The electrodeposition of graphene has drawn considerable attention due to its appealing applications for sensors, supercapacitors and lithium-ion batteries. However, there are still some limitations in the current electrodeposition methods for graphene. Here, we present a novel electrodeposition method for the direct deposition of reduced graphene oxide (rGO) with chitosan. In this method, a 2-hydroxypropyltrimethylammonium chloride-based chitosan-modified rGO material was prepared. This material disperses homogenously in the chitosan solution, forming a deposition solution with good dispersion stability. Subsequently, the modified rGO material was deposited on an electrode through codeposition with chitosan, based on the coordination deposition method. After electrodeposition, the homogeneous, deposited rGO/chitosan films can be generated on copper or silver electrodes or substrates. The electrodeposition method allows for the convenient and controlled creation of rGO/chitosan nanocomposite coatings and films of different shapes and thickness. It also introduces a new method of creating films, as they can be peeled completely from the electrodes. Moreover, this method allows for a rGO/chitosan film to be deposited directly onto an electrode, which can then be used for electrochemical detection. PMID:29765797

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

EPA Science Inventory

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

A delafossite-based copper catalyst for sustainable Cl2 production by HCl oxidation.

PubMed

Mondelli, Cecilia; Amrute, Amol P; Schmidt, Timm; Pérez-Ramírez, Javier

2011-07-07

A copper catalyst based on a delafossite precursor (CuAlO(2)) displays high activity and extraordinary lifetime in the gas-phase oxidation of HCl to Cl(2), representing a cost-effective alternative to RuO(2)-based catalysts for chlorine recycling. This journal is © The Royal Society of Chemistry 2011

Real-time oxide evolution of copper protected by graphene and boron nitride barriers.

PubMed

Galbiati, M; Stoot, A C; Mackenzie, D M A; Bøggild, P; Camilli, L

2017-01-09

Applying protective or barrier layers to isolate a target item from the environment is a common approach to prevent or delay its degradation. The impermeability of two-dimensional materials such as graphene and hexagonal boron nitride (hBN) has generated a great deal of interest in corrosion and material science. Owing to their different electronic properties (graphene is a semimetal, whereas hBN is a wide-bandgap insulator), their protection behaviour is distinctly different. Here we investigate the performance of graphene and hBN as barrier coatings applied on copper substrates through a real-time study in two different oxidative conditions. Our findings show that the evolution of the copper oxidation is remarkably different for the two coating materials.

Effects of ultrasound and temperature on copper electro reduction in Deep Eutectic Solvents (DES).

PubMed

Mandroyan, Audrey; Mourad-Mahmoud, Mahmoud; Doche, Marie-Laure; Hihn, Jean-Yves

2014-11-01

This paper concerns a preliminary study for a new copper recovery process from ionic solvent. The aim of this work is to study the reduction of copper in Deep Eutectic Solvent (choline chloride-ethylene glycol) and to compare the influence of temperature and the ultrasound effects on kinetic parameters. Solutions were prepared by dissolution of chloride copper salt CuCl2 (to obtain Copper in oxidation degree II) or CuCl (to obtain Copper in oxidation degree I) and by leaching metallic copper directly in DES. The spectrophotometry UV-visible analysis of the leached solution showed that the copper soluble form obtained is at oxidation degree I (Copper I). Both cyclic voltammetry and linear voltammetry were performed in the three solutions at three temperatures (25, 50 and 80°C) and under ultrasonic conditions (F=20kHz, PT=5.8W) to calculate the mass transfer diffusion coefficient kD and the standard rate coefficient k°. These parameters are used to determine that copper reduction is carried out via a mixed kinetic-diffusion control process. Temperature and ultrasound have the same effect on mass transfer for reduction of Cu(II)/Cu(I). On the other hand, temperature is more beneficial than ultrasound for mass transfer of Cu(I)/Cu. Standard rate constant improvement due to temperature increase is of the same order as that obtained with ultrasound. But, by combining higher temperature and ultrasound (F=20kHz, PT=5.6W at 50°C), reduction limiting current is increased by a factor of 10 compared to initial conditions (T=25°C, silent), because ultrasonic stirring is more efficient in lower viscosity fluid. These values can be considered as key-parameters in the design of copper recovery in global processes using ultrasound. Copyright © 2014 Elsevier B.V. All rights reserved.

Old iron, young copper: from Mars to Venus.

PubMed

Crichton, R R; Pierre, J L

2001-06-01

Iron and copper are metals which play an important role in the living world. From a brief consideration of their chemistry and biochemistry we conclude that the early chemistry of life used water soluble ferrous iron while copper was in the water-insoluble Cu(I) state as highly insoluble sulphides. The advent of oxygen was a catastrophic event for most living organisms, and can be considered to be the first general irreversible pollution of the earth. In contrast to the oxidation of iron and its loss of bioavailability as insoluble Fe(III), the oxidation of insoluble Cu(I) led to soluble Cu(II). A new iron biochemistry became possible after the advent of oxygen, with the development of chelators of Fe(III), which rendered iron once again accessible, and with the control of the potential toxicity of iron by its storage in a water soluble, non-toxic, bio-available storage protein (ferritin). Biology also discovered that whereas enzymes involved in anaerobic metabolism were designed to operate in the lower portion of the redox spectrum, the arrival of dioxygen created the need for a new redox active metal which could attain higher redox potentials. Copper, now bioavailable, was ideally suited to exploit the oxidizing power of dioxygen. The arrival of copper also coincided with the development of multicellular organisms which had extracellular cross-linked matrices capable of resisting attack by oxygen free radicals. After the initial 'iron age' subsequent evolution moved, not towards a 'copper age', but rather to an 'iron-copper' age. In the second part of the review, this symbiosis of iron and copper is examined in yeast. We then briefly consider iron and copper metabolism in mammals, before looking at iron-copper interactions in mammals, particularly man, and conclude with the reflection that, as in Greek and Roman mythology, a better understanding of the potentially positive interactions between Mars (iron) and Venus (copper) can only be to the advantage of our species.

Solar photochemical oxidation of alcohols using catalytic hydroquinone and copper nanoparticles under oxygen: oxidative cleavage of lignin models.

PubMed

Mitchell, Lorna J; Moody, Christopher J

2014-11-21

Alcohols are converted into to their corresponding carbonyl compounds using catalytic amounts of 1,4-hydroquinone with a copper nanoparticle electron transfer mediator with oxygen as the terminal oxidant in acetone as solvent under visible light irradiation. These conditions employing biorenewable hydroquinone as reagent were developed from initial experiments using stoichiometric amounts of 1,4-benzoquinone as oxidant. A range of benzylic and aliphatic primary and secondary alcohols are oxidized, affording the corresponding aldehydes or ketones in moderate to excellent yields. The methodology is also applicable to the oxidative degradation of lignin model compounds that undergo C-C bond cleavage to give simple aromatic compounds.

Nitric oxide donors or nitrite counteract copper-[dithiocarbamate](2)-mediated tumor cell death and inducible nitric oxide synthase down-regulation: possible role of a nitrosyl-copper [dithiocarbamate](2) complex.

PubMed

Rhenals, Maricela Viola; Strasberg-Rieber, Mary; Rieber, Manuel

2010-02-25

In contrast to other metal-dithiocarbamate [DEDTC] complexes, the copper-DEDTC complex is highly cytotoxic, inducing oxidative stress, preferentially in tumor cells. Because nitric oxide (NO) forms adducts with Cu[DEDTC](2), we investigated whether NO donors like S-nitroso-N-acetyl penicillamine (SNAP) or sodium nitroprusside (SNP), and nitrite, a NO decomposition product, modulate Cu[DEDTC](2) cytotoxicity against human tumor cells. We show that apoptosis-associated PARP cleavage and inducible nitric oxide synthase (iNOS) down-regulation induced by nanomolar Cu[DEDTC](2), are counteracted by 50 muM SNAP, SNP, or CoCl(2), an inducer of hypoxia and NO signaling. Nitrite was stochiometrically effective in antagonizing Cu[DEDTC](2) cytotoxicity and inducing shifts in the absorption spectrum of the binary complex in the 280 and 450 nm regions. Subtoxic concentrations of Cu[DEDTC](2) became lethal when tumor cells were pretreated with c-PTIO, a membrane-impermeable scavenger for extracellular NO. Our results suggest that: (a) reactive oxygen species induced by Cu[DEDTC](2) are scavenged by nitrite released from NO, (b) the extent of lethality of Cu[DEDTC](2) is dependent on the reciprocal formation of an inactive ternary Cu[DEDTC](2)NO copper-nitrosyl complex.

EXAMINATION OF THE OXIDATION PROTECTION OF ZINC COATINGS FORMED ON COPPER ALLOYS AND STEEL SUBSTRATES

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

Papazoglou, M.; Chaliampalias, D.; Vourlias, G.

2010-01-21

The exposure of metallic components at aggressive high temperature environments, usually limit their usage at similar application because they suffer from severe oxidation attack. Copper alloys are used in a wide range of high-quality indoor and outdoor applications, statue parts, art hardware, high strength and high thermal conductivity applications. On the other hand, steel is commonly used as mechanical part of industrial set outs or in the construction sector due to its high mechanical properties. The aim of the present work is the examination of the oxidation resistance of pack cementation zinc coatings deposited on copper, leaded brass and steelmore » substrates at elevated temperature conditions. Furthermore, an effort made to make a long-term evaluation of the coated samples durability. The oxidation results showed that bare substrates appear to have undergone severe damage comparing with the coated ones. Furthermore, the mass gain of the uncoated samples was higher than this of the zinc covered ones. Particularly zinc coated brass was found to be more resistant to oxidation conditions in which it was exposed as it has the lower mass gain as compared to the bare substrates and zinc coated copper. Zinc coated steel was also proved to be more resistive than the uncoated steel.« less

Three-tier rough superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Cao, Yuanzhi; Yuan, Longyan; Hu, Bin; Zhou, Jun

2015-08-01

A three-tier rough superhydrophobic surface was fabricated by growing hydrophobic modified (fluorinated silane) zinc oxide (ZnO)/copper oxide (CuO) hetero-hierarchical structures on silicon (Si) micro-pillar arrays. Compared with the other three control samples with a less rough tier, the three-tier surface exhibits the best water repellency with the largest contact angle 161° and the lowest sliding angle 0.5°. It also shows a robust Cassie state which enables the water to flow with a speed over 2 m s-1. In addition, it could prevent itself from being wetted by the droplet with low surface tension (mixed water and ethanol 1:1 in volume) which reveals a flow speed of 0.6 m s-1 (dropped from the height of 2 cm). All these features prove that adding another rough tier on a two-tier rough surface could futher improve its water-repellent properties.

Ionic strength and DOC determinations from various freshwater sources to the San Francisco Bay

USGS Publications Warehouse

Hunter, Y.R.; Kuwabara, J.S.

1994-01-01

An exact estimation of dissolved organic carbon (DOC) within the salinity gradient of zinc and copper metals is significant in understanding the limit to which DOC could influence metal speciation. A low-temperature persulfate/oxygen/ultraviolet wet oxidation procedure was utilized for analyzing DOC samples adapted for ionic strength from major freshwater sources of the northern and southern regions of San Francisco Bay. The ionic strength of samples was modified with a chemically defined seawater medium up to 0.7M. Based on the results, a minimum effect of ionic strength on oxidation proficiency for DOC sources to the Bay over an ionic strength gradient of 0.0 to 0.7 M was observed. There was no major impacts of ionic strength on two Suwanee River fulvic acids. In general, the noted effects associated with ionic strength were smaller than the variances seen in the aquatic environment between high- and low-temperature methods.

Three-tier rough superhydrophobic surfaces.

PubMed

Cao, Yuanzhi; Yuan, Longyan; Hu, Bin; Zhou, Jun

2015-08-07

A three-tier rough superhydrophobic surface was fabricated by growing hydrophobic modified (fluorinated silane) zinc oxide (ZnO)/copper oxide (CuO) hetero-hierarchical structures on silicon (Si) micro-pillar arrays. Compared with the other three control samples with a less rough tier, the three-tier surface exhibits the best water repellency with the largest contact angle 161° and the lowest sliding angle 0.5°. It also shows a robust Cassie state which enables the water to flow with a speed over 2 m s(-1). In addition, it could prevent itself from being wetted by the droplet with low surface tension (mixed water and ethanol 1:1 in volume) which reveals a flow speed of 0.6 m s(-1) (dropped from the height of 2 cm). All these features prove that adding another rough tier on a two-tier rough surface could futher improve its water-repellent properties.

Periodate and hypobromite modification of Southern pine wood to improve sorption of copper ion

Treesearch

James D. McSweeny; Roger M. Rowell; George C. Chen; Thomas L. Eberhardt; Min Soo-Hong

2008-01-01

Milled southern pine wood was modified with sequential treatments of sodium periodate and sodium hypobromite for the purpose of improving copper ion (Cu2+) sorption capacity of the wood when tested in 24-h equilibrium batch tests. The modified wood provided additional carboxyl groups to those in the native wood and substantially increased Cu2+ uptake over that of...

Effect of citric acid modification of aspen wood on sorption of copper ion

Treesearch

James D. McSweeny; Roger M. Rowell; Soo Hong Min

2006-01-01

Milled aspen wood was thermochemically modified with citric acid for the purpose of improving the copper (Cu2+) ion sorption capacity of the wood when tested in 24-hour equilibrium batch tests. The wood-citric acid adducts provided additional carboxyl groups to those in the native wood and substantially increased Cu2+ ion uptake of the modified wood compared with that...

Fractionation of heavy metals in liquefied chromated copper arsenate (CCA)-treated wood sludge using a modified BCR-sequential extraction procedure

Treesearch

Hui Pan; Chung-Yun Hse; Robert Gambrell; Todd F. Shupe

2009-01-01

Chromated copper arsenate (CCA)-treated wood was liquefied with polyethylene glycol/glycerin and sulfuric acid. After liquefaction, most CCA metals (98% As, 92% Cr, and 83% Cu) were removed from liquefied CCA-treated wood by precipitation with calcium hydroxide. The original CCA-treated wood and liquefied CCA-treated wood sludge were fractionated by a modified...

Effects of Copper and Selenium Supplementation on Performance and Lipid Metabolism in Confined Brangus Bulls

PubMed Central

Netto, Arlindo Saran; Zanetti, Marcus Antônio; Claro, Gustavo Ribeiro Del; de Melo, Mariza Pires; Vilela, Flávio Garcia; Correa, Lisia Bertonha

2014-01-01

Twenty-eight Brangus cattle were used to determine the effect of copper and selenium supplementation on performance, feed efficiency, composition of fatty acids in Longissimus dorsi (LD) muscle, and cholesterol concentration in serum and in LD muscle and enzymes activities, reduced glutathione (GSH) and oxidized glutathione (GSSG). The treatments were: i) Control, without copper (Cu) and selenium (Se) supplementation; ii) Se, 2 mg Se/kg of dry matter such as sodium selenite; iii) Cu, 40 mg Cu/kg of dry matter such as copper sulfate; iv) Se/Cu, 2 mg Se/kg of dry matter such as sodium selenite and 40 mg Cu/kg of dry matter such as copper sulfate. LD muscle fatty acid composition was not influenced by the treatments (p>0.05). The serum concentration of cholesterol was not influenced by the treatments (p>0.05), however, the concentration of cholesterol in LD was lower in cattle supplemented with copper and selenium (p<0.05). Oxidized glutathione and reduced glutathione increased (p<0.05) with Cu, Se and Se/Cu supplementation. The supplementation of copper (40 mg/kg DM) and selenium (2 mg/kg DM) altered the metabolism of lipids in confined Brangus cattle, through a decrease in cholesterol deposition in the LD, possibly by changing the ratio between reduced glutathione/oxidized glutathione. Copper and selenium supplementation improved animal performance and feed efficiency (p<0.05) when compared to the control group, providing advantages in the production system, while also benefiting consumers by reducing cholesterol concentration in the meat. PMID:25049978

Hollow nanostructures of metal oxides as next generation electrode materials for supercapacitors.

PubMed

Sharma, Vikas; Singh, Inderjeet; Chandra, Amreesh

2018-01-22

Hollow nanostructures of copper oxides help to stabilize appreciably higher electrochemical characteristics than their solid counter parts of various morphologies. The specific capacitance values, calculated using cyclic voltammetry (CV) and charge-discharge (CD) studies, are found to be much higher than the values reported in literature for copper oxide particles showing  intriguing morphologies or even composites with trendy systems like CNTs, rGO, graphene, etc. The proposed cost-effective synthesis route makes these materials industrially viable for application in alternative energy storage devices. The improved electrochemical response can be attributed to effective access to the higher number of redox sites that become available on the surface, as well as in the cavity of the hollow particles. The ion transport channels also facilitate efficient de-intercalation, which results in the enhancement of cyclability and Coulombic efficiency. The charge storage mechanism in copper oxide structures is also proposed in the paper.

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

PubMed Central

Ugur, Zafer; Gronert, Scott

2017-01-01

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

Element Distribution in the Oxygen-Rich Side-Blow Bath Smelting of a Low-Grade Bismuth-Lead Concentrate

NASA Astrophysics Data System (ADS)

Yang, Tianzu; Xiao, Hui; Chen, Lin; Chen, Wei; Liu, Weifeng; Zhang, Duchao

2018-03-01

Oxygen-rich side-blow bath smelting (OSBS) technology offers an efficient method for processing complex bismuth-lead concentrates; however, the element distributions in the process remain unclear. This work determined the distributions of elements, i.e., bismuth, lead, silver, copper, arsenic and antimony, in an industrial-scale OSBS process. The feed, oxidized slag and final products were collected from the respective sampling points and analyzed. For the oxidative smelting process, 65% of bismuth and 76% of silver in the concentrate report to the metal alloy, whereas less lead reports to the metal ( 31%) than the oxidized slag ( 44%). Approximately 50% of copper enters the matte, while more than 63% of arsenic and antimony report to the slag. For the reductive smelting process, less than 4.5% of bismuth, lead, silver and copper in the oxidized slag enter the reduced slag, indicating high recoveries of these metal values.

Element Distribution in the Oxygen-Rich Side-Blow Bath Smelting of a Low-Grade Bismuth-Lead Concentrate

NASA Astrophysics Data System (ADS)

Yang, Tianzu; Xiao, Hui; Chen, Lin; Chen, Wei; Liu, Weifeng; Zhang, Duchao

2018-06-01

Oxygen-rich side-blow bath smelting (OSBS) technology offers an efficient method for processing complex bismuth-lead concentrates; however, the element distributions in the process remain unclear. This work determined the distributions of elements, i.e., bismuth, lead, silver, copper, arsenic and antimony, in an industrial-scale OSBS process. The feed, oxidized slag and final products were collected from the respective sampling points and analyzed. For the oxidative smelting process, 65% of bismuth and 76% of silver in the concentrate report to the metal alloy, whereas less lead reports to the metal ( 31%) than the oxidized slag ( 44%). Approximately 50% of copper enters the matte, while more than 63% of arsenic and antimony report to the slag. For the reductive smelting process, less than 4.5% of bismuth, lead, silver and copper in the oxidized slag enter the reduced slag, indicating high recoveries of these metal values.

Analyzing the electrooxidation of ethylene glycol and glucose over platinum-modified gold electrocatalysts in alkaline electrolyte using in-situ infrared spectroscopy

NASA Astrophysics Data System (ADS)

Mahoney, Elizabeth G.; Sheng, Wenchao; Cheng, Mei; Lee, Kevin X.; Yan, Yushan; Chen, Jingguang G.

2016-02-01

Platinum modified gold (Pt/Au) catalysts are evaluated for the electrooxidation of ethylene glycol (EG) and glucose (Glc). The Pt/Au catalysts are synthesized on an Au disk and supported Au/C particles through the galvanic displacement of a copper monolayer with Pt. The Pt/Au catalysts are compared to monometallic Pt and Au catalysts for the oxidation of EG and Glc in alkaline electrolyte. The Pt/Au disk has an onset potential for these reactions that is similar to Pt and is lower than Au. The supported catalysts are less active toward the electrooxidation of EG and Glc than the corresponding disk electrodes, but the Pt/Au/C also has an onset potential similar to Pt/C. In-situ FTIR is used to analyze the C-C bond scission in both reactions on the surfaces of Pt, Au, and Pt/Au disks. While the Pt/Au disk is found to have a low onset potential for the oxidation of EG, it does not produce as much CO2 as bulk Pt. On the other hand, the FTIR results show that CO2 is produced for the oxidation of Glc on the Pt/Au disk. These results show promise for the possibility of decreasing the amount of Pt needed for the electrooxidation of polyol molecules.

Copper(II)-catalyzed oxidative [3+2] cycloaddition reactions of secondary amines with α-diazo compounds: a facile and efficient synthesis of 1,2,3-triazoles.

PubMed

Li, Yi-Jin; Li, Xue; Zhang, Shao-Xiao; Zhao, Yu-Long; Liu, Qun

2015-07-25

A novel copper-catalyzed [3+2] cycloaddition reaction of secondary amines with α-diazo compounds has been developed via a cross-dehydrogenative coupling process. The reaction involves a sequential aerobic oxidation/[3+2] cycloaddition/oxidative aromatization procedure and provides an efficient method for the construction of 1,2,3-triazoles in a single step in an atom-economic manner from readily available starting materials under very mild conditions.

Electrical characterization of anodic alumina substrate with via-in-pad structure

NASA Astrophysics Data System (ADS)

Kim, Moonjung

2013-10-01

An anodic alumina substrate has been developed as a package substrate for dynamic random access memory devices. Unlike the conventional package substrates commonly made by laminating an epoxy-based core and cladding with copper, this substrate is fabricated using aluminum anodization technology. The anodization process produces a thick aluminum oxide layer on the aluminum substrate to be used as a dielectric layer. Placing copper patterns on the anodic aluminum oxide layer forms a new substrate structure that consists of a layered structure of aluminum, anodic aluminum oxide, and copper. Using selective anodization in the fabrication process, a via structure connecting the top copper layer and bottom aluminum layer is demonstrated. Additionally, by putting vias directly in the bond and ball pads in the substrate design, the via-in-pad structure is applied in this work. These two-layer metal structures and via-in-pad arrangements make routing easier and thus provide more design flexibility. Additionally, this new package substrate has improved the power distribution network impedance given the characteristics of these structures.

Altered serum copper homeostasis suggests higher oxidative stress and lower antioxidant capability in patients with chronic hepatitis B.

PubMed

Huang, Yansong; Zhang, Yuan; Lin, Zhexuan; Han, Ming; Cheng, Hongqiu

2018-06-01

Copper homeostasis can be altered by inflammation. This study aimed to investigate the alteration of serum copper homeostasis and to explore its clinical significance in patients with chronic hepatitis B (CHB).Thirty-two patients with CHB and 10 aged- and sex-matched healthy controls were recruited. Analyses included serum levels of total copper (TCu), copper ions (Cu), small molecule copper (SMC), ceruloplasmin (CP), Cu/Zn superoxide dismutase 1 (SOD1), urinary copper, and the activities of serum CP and SOD1.The serum TCu and urinary copper levels in patients with CHB were significantly higher than the controls (P = .04 and .003), while the serum Cu was lower than the controls (P = .0002). CP and SOD1 activities in the serum were significantly lower in patients with CHB compared to controls (P = .005) despite higher serum concentrations. In addition, serum alanine aminotransferase inversely correlated with serum CP activity (P = .0318, r = -0.4065).Serum copper homeostasis was altered in this cohort of patients with CHB. The results suggest increased oxidative stress and impaired antioxidant capability in patients with CHB, in addition to necroinflammation. These results may provide novel insights into the diagnosis and treatment of patients with CHB.

Study of sintering behavior of vapor forms of 1-octanethiol coated copper nanoparticles for application to ink-jet printing technology.

PubMed

Kwon, Jinhyeong; Park, Shinyoung; Haque, Md Mominul; Kim, Young-Seok; Lee, Caroline Sunyong

2012-04-01

Sub-50 nm copper nanoparticles coated with sub-5 nm 1-octanethiol layer for oxidation inhibition were examined to confirm the 1-octanethiol removal temperature as the sub-50 nm copper nanoparticles are sintered. As a result, 1-octanethiol Self-Assembled Multi-layers (SAMs) on sub-50 nm copper nanoparticles were successfully removed before sintering of copper nanoparticles so that a high density of copper line could be obtained. Finally, the line resistivity was measured and compared to verify the effect of sintering in different atmospheres. As a result, electrical resistivity of the copper pattern sintered in hydrogen atmosphere was measured at 6.96 x 10(-6) ohm-cm whereas that of the copper pattern sintered in mixed gas atmosphere was measured at 2.62 x 10(-5) ohm-cm. Thus, sintering of copper patterns was successfully done to show low electrical resistivity values. Moreover, removal of 1-octanethiol coating after sintering process was confirmed using X-ray photoelectron spectroscopy (XPS) analysis. By showing no sulfur content, XPS results indicate that 1-octanethiol is completely removed. Therefore, the vapor form of 1-octanethiol coating layers can be safely used as an oxidation inhibition layer for low temperature sintering processes and ink-jet applications.

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 four-helix bundle stores copper for methane oxidation

PubMed Central

Vita, Nicolas; Platsaki, Semeli; Baslé, Arnaud; Allen, Stephen J.; Paterson, Neil G.; Crombie, Andrew T.; Murrell, J. Colin; Waldron, Kevin J.; Dennison, Christopher

2015-01-01

Methane-oxidising bacteria (methanotrophs) require large quantities of copper for the membrane-bound (particulate) methane monooxygenase (pMMO)1,2. Certain methanotrophs are also able to switch to using the iron-containing soluble MMO (sMMO) to catalyse methane oxidation, with this switchover regulated by copper3,4. MMOs are Nature’s primary biological mechanism for suppressing atmospheric levels of methane, a potent greenhouse gas. Furthermore, methanotrophs and MMOs have enormous potential in bioremediation and for biotransformations producing bulk and fine chemicals, and in bioenergy, particularly considering increased methane availability from renewable sources and hydraulic fracturing of shale rock5,6. We have discovered and characterised a novel copper storage protein (Csp1) from the methanotroph Methylosinus trichosporium OB3b that is exported from the cytosol, and stores copper for pMMO. Csp1 is a tetramer of 4-helix bundles with each monomer binding up to 13 Cu(I) ions in a previously unseen manner via mainly Cys residues that point into the core of the bundle. Csp1 is the first example of a protein that stores a metal within an established protein-folding motif. This work provides a detailed insight into how methanotrophs accumulate copper for the oxidation of methane. Understanding this process is essential if the wide-ranging biotechnological applications of methanotrophs are to be realised. Cytosolic homologues of Csp1 are present in diverse bacteria thus challenging the dogma that such organisms do not use copper in this location. PMID:26308900

Copper enhances the activity and salt resistance of mixed methane-oxidizing communities.

PubMed

van der Ha, David; Hoefman, Sven; Boeckx, Pascal; Verstraete, Willy; Boon, Nico

2010-08-01

Effluents of anaerobic digesters are an underestimated source of greenhouse gases, as they are often saturated with methane. A post-treatment with methane-oxidizing bacterial consortia could mitigate diffuse emissions at such sites. Semi-continuously fed stirred reactors were used as model systems to characterize the influence of the key parameters on the activity of these mixed methanotrophic communities. The addition of 140 mg L(-1) NH (4) (+) -N had no significant influence on the activity nor did a temperature increase from 28 degrees C to 35 degrees C. On the other hand, addition of 0.64 mg L(-1) of copper(II) increased the methane removal rate by a factor of 1.5 to 1.7 since the activity of particulate methane monooxygenase was enhanced. The influence of different concentrations of NaCl was also tested, as effluents of anaerobic digesters often contain salt levels up to 10 g NaCl L(-1). At a concentration of 11 g NaCl L(-1), almost no methane-oxidizing activity was observed in the reactors without copper addition. Yet, reactors with copper addition exhibited a sustained activity in the presence of NaCl. A colorimetric test based on naphthalene oxidation showed that soluble methane monooxygenase was inhibited by copper, suggesting that the particulate methane monooxygenase was the active enzyme and thus more salt resistant. The results obtained demonstrate that the treatment of methane-saturated effluents, even those with increased ammonium (up to 140 mg L(-1) NH (4) (+) -N) and salt levels, can be mitigated by implementation of methane-oxidizing microbial consortia.

Synthesis of highly phase pure (Bi, Pb)-Sr-Ca-Cu-O superconductor

DOEpatents

Dorris, S.E.; Poeppel, R.B.; Prorok, B.C.; Lanagan, M.T.; Maroni, V.A.

1994-10-11

An article and method of manufacture of (Bi,Pb)-Sr-Ca-Cu-O superconductor are disclosed. The superconductor is manufactured by preparing a first powdered mixture of bismuth oxide, lead oxide, strontium carbonate, calcium carbonate and copper oxide. A second powdered mixture is then prepared of strontium carbonate, calcium carbonate and copper oxide. The mixtures are calcined separately with the two mixtures then combined. The resulting combined mixture is then subjected to a powder in tube deformation and thermal processing to produce a substantially phase pure (Bi,Pb)-Sr-Ca-Cu-O superconductor. 5 figs.

Some Characteristics of Free Cell Population in the Airways of Rats after Intratracheal Instillation of Copper-Containing Nano-Scale Particles

PubMed Central

Privalova, Larisa I.; Katsnelson, Boris A.; Loginova, Nadezhda V.; Gurvich, Vladimir B.; Shur, Vladimir Y.; Beikin, Yakov B.; Sutunkova, Marina P.; Minigalieva, Ilzira A.; Shishkina, Ekaterina V.; Pichugova, Svetlana V.; Tulakina, Ludmila G.; Beljayeva, Svetlana V.

2014-01-01

We used stable water suspensions of copper oxide particles with mean diameter 20 nm and of particles containing copper oxide and element copper with mean diameter 340 nm to assess the pulmonary phagocytosis response of rats to a single intratracheal instillation of these suspensions using optical, transmission electron, and semi-contact atomic force microscopy and biochemical indices measured in the bronchoalveolar lavage fluid. Although both nano and submicron ultrafine particles were adversely bioactive, the former were found to be more toxic for lungs as compared with the latter while evoking more pronounced defense recruitment of alveolar macrophages and especially of neutrophil leukocytes and more active phagocytosis. Based on our results and literature data, we consider both copper solubilization and direct contact with cellular organelles (mainly, mitochondria) of persistent particles internalized by phagocytes as probable mechanisms of their cytotoxicity. PMID:25421246

Effects of Copper Oxide Nanoparticles on Antioxidant Enzyme Activities and on Tissue Accumulation of Oreochromis niloticus.

PubMed

Tunçsoy, Mustafa; Duran, Servet; Ay, Özcan; Cicik, Bedii; Erdem, Cahit

2017-09-01

Accumulation of copper oxide nanoparticles (CuO NPs) in gill, liver and muscle tissues of Oreochromis niloticus and its effects on superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) activities in gill and liver tissues were studied after exposing the fish to 20 µg/L Cu over 15 days. Copper levels and enzyme activities in tissues were determined using spectrophotometric (ICP-AES and UV) techniques respectively. No mortality was observed during the experiments. Copper levels increased in gill and liver tissues of O. niloticus compared to control when exposed to CuO NPs whereas exposure to metal had no effect on muscle level at the end of the exposure period. Highest accumulation of copper was observed in liver while no accumulation was detected in muscle tissue. SOD, CAT activities decreased and GPx activity increased in gill and liver tissues when exposed to CuO NPs.

The bioleaching potential of a bacterial consortium.

PubMed

Latorre, Mauricio; Cortés, María Paz; Travisany, Dante; Di Genova, Alex; Budinich, Marko; Reyes-Jara, Angélica; Hödar, Christian; González, Mauricio; Parada, Pilar; Bobadilla-Fazzini, Roberto A; Cambiazo, Verónica; Maass, Alejandro

2016-10-01

This work presents the molecular foundation of a consortium of five efficient bacteria strains isolated from copper mines currently used in state of the art industrial-scale biotechnology. The strains Acidithiobacillus thiooxidans Licanantay, Acidiphilium multivorum Yenapatur, Leptospirillum ferriphilum Pañiwe, Acidithiobacillus ferrooxidans Wenelen and Sulfobacillus thermosulfidooxidans Cutipay were selected for genome sequencing based on metal tolerance, oxidation activity and bioleaching of copper efficiency. An integrated model of metabolic pathways representing the bioleaching capability of this consortium was generated. Results revealed that greater efficiency in copper recovery may be explained by the higher functional potential of L. ferriphilum Pañiwe and At. thiooxidans Licanantay to oxidize iron and reduced inorganic sulfur compounds. The consortium had a greater capacity to resist copper, arsenic and chloride ion compared to previously described biomining strains. Specialization and particular components in these bacteria provided the consortium a greater ability to bioleach copper sulfide ores. Copyright © 2016 Elsevier Ltd. All rights reserved.

Amperometric sensing of hydrogen peroxide using glassy carbon electrode modified with copper nanoparticles

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

Sophia, J.; Muralidharan, G., E-mail: muraligru@gmail.com

2015-10-15

In this paper, fabrication of glassy carbon electrode (GCE) modified with nano copper particles is discussed. The modified electrode has been tested for the non-enzymatic electrochemical detection of hydrogen peroxide (H{sub 2}O{sub 2}). The copper nanoparticles (Cu NPs) were prepared employing a simple chemical reduction method. The presence of Cu NPs was confirmed through UV–visible (UV–vis) absorption spectroscopy and X-ray diffraction (XRD) analysis. The size and morphology of the particles were investigated using transmission electron microscopy (TEM). The electrochemical properties of the fabricated sensor were studied via cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The electrochemical sensor displayedmore » excellent performance features towards H{sub 2}O{sub 2} detection exhibiting wide linear range, low detection limit, swift response time, good reproducibility and stability.« less

Low temperature processing of dielectric perovskites for energy storage

NASA Astrophysics Data System (ADS)

Singh, N. B.; Schreib, Ben; Devilbiss, Michael; Loiacono, Julian; Arnold, Bradley; Choa, Fow-Sen; Mandal, K. D.

2016-05-01

Since the report of high dielectric value was published for the calcium copper titanate of the stoichiometry CaCu3Ti4O12 (CCTO), several of its analogs such as Yittrium copper titanate Y2/3Cu3Ti4O12 (YCTO), Pr2/3Cu3Ti4O12 (PCTO) and several other compounds have been studied extensively. Most of these materials have demonstrated very high dielectric constants. However, the roadblock is their low resistivity. To overcome this problem, several approaches have been considered, including doping and substitution. In order to solve this problem, we have synthesized the stoichiometric composition and used low temperature processing to grow grains of La2/3Cu3Ti4O12 (LCTO) stoichiometric compound. LCTO with excess copper oxide was also prepared to determine its effect on the morphology and dielectric constant of the stoichiometric LCTO compound. In spite of the low melting point of copper oxide, we observed that excess copper oxide did not show any faster grain growth. Also, the dielectric constant of LCTO was lower than CCTO and unlike CCTO, LCTO showed significant changes as the function of frequency. The measured resistivity was slightly higher than CCTO.

Improvement and Evaluation of Copper Oxidation Experimental Procedure for the Introduction of the Law of Definite Proportion

ERIC Educational Resources Information Center

Yamashita, Shuichi; Kashiwaguma, Yasuyuki; Hayashi, Hideko; Pietzner, Verena

2017-01-01

In science classes, students usually learn about the law of definite proportions by the oxidation of copper. However, common procedures usually do not lead to proper results. This leads to confusion among the students because their experimental results do not fit to the theoretical values. Therefore, we invented a new procedure for this experiment…

Remarkable co-catalysis by copper(I) oxide in the palladium catalyzed cross-coupling of arylboronic acids with ethyl bromoacetate.

PubMed

Liu, Xing-xin; Deng, Min-zhi

2002-03-21

Copper(I) oxide can effectively co-catalyze the Suzuki type cross-coupling reactions of arylboronic acids with ethyl bromoacetate. As an alternative protocol for introducing the methylenecarboxy group into functionalized molecules, this reaction occurs in the absence of highly toxic thallium compounds or special ligands and should be convenient and practical.

Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO 2 conversion

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

Halder, Avik; Kilianová, Martina; Yang, Bing

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst's restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the startingmore » nano catalyst is composed of iron oxides differing in chemical nature (alpha-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of alpha-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.« less

Sulfidation treatment of copper-containing plating sludge towards copper resource recovery.

PubMed

Kuchar, D; Fukuta, T; Onyango, M S; Matsuda, H

2006-11-02

The present study is concerned with the sulfidation treatment of copper-containing plating sludge towards copper resource recovery by flotation of copper sulfide from treated sludge. The sulfidation treatment was carried out by contacting simulated or real copper plating sludge with Na(2)S solution for a period of 5 min to 24 h. The initial molar ratio of S(2-) to Cu(2+) (S(2-) to Me(2+) in the case of real sludge) was adjusted to 1.00, 1.25 or 1.50, while the solid to liquid ratio was set at 1:50. As a result, it was found that copper compounds were converted to various copper sulfides within the first 5 min. In the case of simulated copper sludge, CuS was identified as the main sulfidation product at the molar ratio of S(2-) to Cu(2+) of 1.00, while Cu(7)S(4) (Roxbyite) was mainly found at the molar ratios of S(2-) to Cu(2+) of 1.50 and 1.25. Based on the measurements of oxidation-reduction potential, the formation of either CuS or Cu(7)S(4) at different S(2-) to Cu(2+) molar ratios was attributed to the changes in the oxidation-reduction potential. By contrast, in the case of sulfidation treatment of real copper sludge, CuS was predominantly formed, irrespective of S(2-) to Me(2+) molar ratio.

Simultaneous determination of isoproterenol, acetaminophen, folic acid, propranolol and caffeine using a sensor platform based on carbon black, graphene oxide, copper nanoparticles and PEDOT:PSS.

PubMed

Wong, Ademar; Santos, Anderson Martin; Silva, Tiago Almeida; Fatibello-Filho, Orlando

2018-06-01

We explored the use of carbon black (CB), graphene oxide (GO), copper nanoparticles (CuNPs) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) as electrode materials for the simultaneous determination of isoproterenol, acetaminophen, folic acid, propranolol and caffeine. The designed nanostructured surface was widely characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), contact angle measurements and electrochemistry. From electrochemical characterization assays carried out towards the potassium ferricyanide redox probe, fast electron transfer kinetics and a considerably higher electroactive surface area were observed for the modified electrodic surface based on CB, GO, CuNPs and PEDOT:PSS film. Using square-wave voltammetry (SWV), well defined and resolved anodic peaks were detected for isoproterenol, acetaminophen, folic acid, propranolol and caffeine, with peak-to-peak potential separation not less than 170 mV. Then, the SWV technique was explored for the simultaneous determination of quinary mixtures of these analytes, resulting in analytical curves with linear ranges and limits of detection at micromolar concentration levels. The practical viability of the proposed voltammetric sensor was illustrated in the analysis of human body fluid samples. The proposed sensor showed good repeatability and a successful application using urine and serum matrices, with recoveries close to 100%. Copyright © 2018 Elsevier B.V. All rights reserved.

Research on the effect of alkali roasting of copper dross on leaching rate of indium

NASA Astrophysics Data System (ADS)

Dafang, Liu; Fan, Xingxiang; Shi, Yifeng; Yang, Kunbin

2017-11-01

The byproduct copper dross produced during refining crude lead was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and fluorescence spectrometer (XRF), which showed that copper dross mainly contained lead, copper, zinc, arsenic, antimony, bismuth, sulfur and a small amount of indium and silver etc. The mineralogical phase change of oxidation roasting of copper dross by adding sodium hydroxide was analyzed with the help of XRD and SEM. The effects of water leaching, ratio of sodium hydroxide, roasting time, and roasting temperature on leaching rate of indium were investigated mainly. The experimental results showed that phase of lead metal and sulfides of lead, copper and zinc disappeared after oxidation roasting of copper dross by adding sodium hydroxide, new phase of oxides of lead, copper, zinc and sodium salt of arsenic and antimony appeared. Water leaching could remove arsenic, and acid leaching residue obtained was then leached with acid. The leaching rate of indium was higher 6.98% compared with alkali roasting of copper dross-acid leaching. It showed that removing arsenic by water leaching and acid leaching could increase the leaching rate of indium and be beneficial to reducing subsequent acid consumption of extracting indium by acid leaching. The roasting temperature had a significant effect on the leaching rate of indium, and leaching rate of indium increased with the rise of roasting temperature. When roasting temperature ranged from 450°C to 600°C, leaching rate of indium increased significantly with the rise of roasting temperature. When roasting temperature rose from 450°C to 600°C, leaching rate of indium increased by 60.29%. The amount of sodium hydroxide had an significant effect on the leaching rate of indium, and the leaching of indium increased with the increase of the amount of sodium hydroxide, and the leaching rate of indium was obviously higher than that of copper dross blank roasting and acid leaching.

Elaboration of Copper-Oxygen Mediated C–H Activation Chemistry in Consideration of Future Fuel and Feedstock Generation

PubMed Central

Lee, Jung Yoon; Karlin, Kenneth D

2015-01-01

To contribute solutions for current energy concerns, improvements in the efficiency of C-H bond cleavage chemistry, e.g., selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. PMID:25756327

Aloe barbadensis Miller mediated green synthesis of mono-disperse copper oxide nanoparticles: Optical properties

NASA Astrophysics Data System (ADS)

Gunalan, Sangeetha; Sivaraj, Rajeshwari; Venckatesh, Rajendran

2012-11-01

In this paper, we report on the synthesis of nanostructured copper oxide particles by both chemical and biological method. A facile and efficient synthesis of copper oxide nanoparticles was carried out with controlled surface properties via green chemistry approach. The CuO nanoparticles synthesized are monodisperse and versatile and were characterized with the help of UV-Vis, PL, FT-IR, XRD, SEM, and TEM techniques. The particles are crystalline in nature and average sizes were between 15 and 30 nm. The morphology of the nanoparticles can be controlled by tuning the amount of Aloe vera extract. This new eco-friendly approach of synthesis is a novel, cheap, and convenient technique suitable for large scale commercial production and health related applications of CuO nanoparticles.

A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.

PubMed

Xu, Boran; Lumb, Jean-Philip; Arndtsen, Bruce A

2015-03-27

The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Bis(1,2-Dimethylimidazole)Copper(I)Hexafluorophosphate: An Experiment Using a Glove Box

ERIC Educational Resources Information Center

Niewahner, J. H.; Walters, Keith A.

2007-01-01

A detailed description of the synthesis of bis(1,2-dimethylimidazole)copper(I) hexafluorophosphate by using techniques in a glove box is presented. The results shows that the synthesis of the copper complex has a distinct color change indicating by-product oxidation by oxygen.

Thiol-based copper handling by the copper chaperone Atox1.

PubMed

Hatori, Yuta; Inouye, Sachiye; Akagi, Reiko

2017-04-01

Human antioxidant protein 1 (Atox1) plays a crucial role in cellular copper homeostasis. Atox1 captures cytosolic copper for subsequent transfer to copper pumps in trans Golgi network, thereby facilitating copper supply to various copper-dependent oxidereductases matured within the secretory vesicles. Atox1 and other copper chaperones handle cytosolic copper using Cys thiols which are ideal ligands for coordinating Cu(I). Recent studies demonstrated reversible oxidation of these Cys residues in copper chaperones, linking cellular redox state to copper homeostasis. Highlighted in this review are unique redox properties of Atox1 and other copper chaperones. Also, summarized are the redox nodes in the cytosol which potentially play dominant roles in the redox regulation of copper chaperones. © 2016 IUBMB Life, 69(4):246-254, 2017. © 2017 International Union of Biochemistry and Molecular Biology.

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

PubMed

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

2018-02-02

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

The decomposition of mixed oxide Ag2Cu2O3: Structural features and the catalytic properties in CO and C2H4 oxidation

NASA Astrophysics Data System (ADS)

Svintsitskiy, Dmitry A.; Kardash, Tatyana Yu.; Slavinskaya, Elena M.; Stonkus, Olga A.; Koscheev, Sergei V.; Boronin, Andrei I.

2018-01-01

The mixed silver-copper oxide Ag2Cu2O3 with a paramelaconite crystal structure is a promising material for catalytic applications. The as-prepared sample of Ag2Cu2O3 consisted of brick-like particles extended along the [001] direction. A combination of physicochemical techniques such as TEM, XPS and XRD was applied to investigate the structural features of this mixed silver-copper oxide. The thermal stability of Ag2Cu2O3 was investigated using in situ XRD under different reaction conditions, including a catalytic CO + O2 mixture. The first step of Ag2Cu2O3 decomposition was accompanied by the appearance of ensembles consisting of silver nanoparticles with sizes of 5-15 nm. Silver nanoparticles were strongly oriented to each other and to the surface of the initial Ag2Cu2O3 bricks. Based on the XRD data, it was shown that the release of silver occurred along the a and b axes of the paramelaconite structure. Partial decomposition of Ag2Cu2O3 accompanied by the formation of silver nanoparticles was observed during prolonged air storage under ambient conditions. The high reactivity is discussed as a reason for spontaneous decomposition during Ag2Cu2O3 storage. The full decomposition of the mixed oxide into metallic silver and copper (II) oxide took place at temperatures higher than 300 °C regardless of the nature of the reaction medium (helium, air, CO + O2). Catalytic properties of partially and fully decomposed samples of mixed silver-copper oxide were measured in low-temperature CO oxidation and C2H4 epoxidation reactions.

Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

PubMed

Koepke, Sara J; Light, Kenneth M; VanNatta, Peter E; Wiley, Keaton M; Kieber-Emmons, Matthew T

2017-06-28

Deployment of solar fuels derived from water requires robust oxygen-evolving catalysts made from earth abundant materials. Copper has recently received much attention in this regard. Mechanistic parallels between Cu and single-site Ru/Ir/Mn water oxidation catalysts, including intermediacy of terminal Cu oxo/oxyl species, are prevalent in the literature; however, intermediacy of late transition metal oxo species would be remarkable given the high d-electron count would fill antibonding orbitals, making these species high in energy. This may suggest alternate pathways are at work in copper-based water oxidation. This report characterizes a dinuclear copper water oxidation catalyst, {[(L)Cu(II)] 2 -(μ-OH) 2 }(OTf) 2 (L = Me 2 TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine) in which water oxidation proceeds with high Faradaic efficiency (>90%) and moderate rates (33 s -1 at ∼1 V overpotential, pH 12.5). A large kinetic isotope effect (k H /k D = 20) suggests proton coupled electron transfer in the initial oxidation as the rate-determining step. This species partially dissociates in aqueous solution at pH 12.5 to generate a mononuclear {[(L)Cu(II)(OH)]} + adduct (K eq = 0.0041). Calculations that reproduce the experimental findings reveal that oxidation of either the mononuclear or dinuclear species results in a common dinuclear intermediate, {[LCu(III)] 2 -(μ-O) 2 } 2+ , which avoids formation of terminal Cu(IV)═O/Cu(III)-O • intermediates. Calculations further reveal that both intermolecular water nucleophilic attack and redox isomerization of {[LCu(III)] 2 -(μ-O) 2 } 2+ are energetically accessible pathways for O-O bond formation. The consequences of these findings are discussed in relation to differences in water oxidation pathways between Cu catalysts and catalysts based on Ru, Ir, and Mn.

From nucleation to coalescence of Cu2O islands during in situ oxidation of Cu(001)

NASA Astrophysics Data System (ADS)

Yang, J. C.; Evan, D.; Tropia, L.

2002-07-01

The nucleation, growth, and coalescence of Cu2O islands due to oxidation of Cu(001) films were visualized by in situ ultrahigh-vacuum transmission electron microscopy. We have previously demonstrated that the nucleation and initial growth of copper oxides is dominated by oxygen surface diffusion. These surface models have been extended to quantitatively represent the coalescence behavior of copper oxidation in the framework of the Johnson-Mehl-Avrami-Kolmogorov theory. An excellent agreement exists between the experimental data of nucleation to coalescence with the surface model. The implication could be an alternate paradigm for passivation and oxidation, since classic theories assume uniform film growth.

Thermodynamic investigations on the growth of CuAlO2 delafossite crystals

NASA Astrophysics Data System (ADS)

Wolff, Nora; Klimm, Detlef; Siche, Dietmar

2018-02-01

Simultaneous differential thermal analysis (DTA) and thermogravimetric (TG) measurements with copper oxide/aluminum oxide mixtures were performed in atmospheres with varying oxygen partial pressures and with crucibles made of different materials. Only sapphire and platinum crucibles proved to be stable under conditions that are useful for the growth of CuAlO2 delafossite single crystals. Then the ternary phase diagram Al2O3-CuO-Cu and its isopleth section Cu2O-Al2O3 were redetermined. Millimeter sized crystals could be obtained from copper oxide melts with 1-2 mol% addition of aluminum oxide that are stable in platinum crucibles held in oxidizing atmosphere containing 15-21% oxygen.

Immobilization of Magnetic Nanoparticles onto Amine-Modified Nano-Silica Gel for Copper Ions Remediation

PubMed Central

Elkady, Marwa; Hassan, Hassan Shokry; Hashim, Aly

2016-01-01

A novel nano-hybrid was synthesized through immobilization of amine-functionalized silica gel nanoparticles with nanomagnetite via a co-precipitation technique. The parameters, such as reagent concentrations, reaction temperature and time, were optimized to accomplish the nano-silica gel chelating matrix. The most proper amine-modified silica gel nanoparticles were immobilized with magnetic nanoparticles. The synthesized magnetic amine nano-silica gel (MANSG) was established and characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and vibrating sample magnetometry (VSM). The feasibility of MANSG for copper ions’ remediation from wastewater was examined. MANSG achieves a 98% copper decontamination from polluted water within 90 min. Equilibrium sorption of copper ions onto MANSG nanoparticles obeyed the Langmuir equation compared to the Freundlich, Temkin, Elovich and Dubinin-Radushkevich (D-R) equilibrium isotherm models. The pseudo-second-order rate kinetics is appropriate to describe the copper sorption process onto the fabricated MANSG. PMID:28773583

Characterization and growth analysis of two types of thin films formed on copper surfaces: An inorganic chromium containing film and an organic film formed via reduction of diazonium ions

NASA Astrophysics Data System (ADS)

Hurley, Belinda Louise

Surface enhanced Raman scattering was used to observe interactions of dilute CrVI solutions with silver and copper surfaces in situ. Using silver as a model surface, CrIII was observed at the near monolayer level, and the spectra were compared to those from CrIII oxyhydroxide species and CrIII/Cr VI mixed oxide. Similar experiments were conducted with copper surfaces and 785 nm excitation. Upon exposure of a copper surface to CrVI solution, the characteristic copper oxide Raman bands disappeared, and a Cr III band increased in intensity over a period of ˜20 hours. The intensity of the CrIII band on copper became self limiting after the formation of several CrIII monolayers, as supported by chronoamperometry experiments. This CrIII spectrum was stable after CrVI was removed from the solution provided the potential remained negative of -200 mV vs. Ag/AgCl. The results support the conclusion that CrVI is reductively adsorbed to copper at the near neutral pH and open circuit potentials expected for Cu/Al alloys in field applications. The CrIII film is stable and strongly inhibits oxygen reduction at the treated copper surface. Copper surfaces and polished Aluminum Alloy 2024 T3 substrates were derivatized at open circuit potential with arenediazonium salts in both aprotic and aqueous media. Raman spectroscopy confirmed the presence of a derivatized film on the substrates before and after exposure to boiling water and sonication in acetone. Preliminary experiments to test these films for corrosion inhibition proved unsuccessful. Aluminum and copper substrates were prepared and used for x-ray photoelectron spectroscopy (XPS) analysis of the derivatization results. In the copper experiments, one surface was native oxide copper, predominantly in the form of Cu2O, and one surface was predominantly Cu 0. Results of the XPS analysis indicate the presence of a Cu-O-C linkage and possibly a Cu-C covalent bond between the aryl ring and the copper substrate. XPS results also indicate the formation of multilayers on both types of copper surfaces with different percentages of azo coupling within the multilayers on the two surfaces. These easily prepared, covalently bonded organic films could be used for applications currently fulfilled with self-absorbed monolayers and Langmuir Blodgett films.

[Effects of copper on biodegradation mechanism of trichloroethylene by mixed microorganisms].

PubMed

Gao, Yanhui; Zhao, Tiantao; Xing, Zhilin; He, Zhi; Zhang, Lijie; Peng, Xuya

2016-05-25

We isolated and enriched mixed microorganisms SWA1 from landfill cover soils supplemented with trichloroethylene (TCE). The microbial mixture could degrade TCE effectively under aerobic conditions. Then, we investigated the effect of copper ion (0 to 15 μmol/L) on TCE biodegradation. Results show that the maximum TCE degradation speed was 29.60 nmol/min with 95.75% degradation when copper ion was at 0.03 μmol/L. In addition, genes encoding key enzymes during biodegradation were analyzed by Real-time quantitative reverse transcription PCR (RT-qPCR). The relative expression abundance of pmoA gene (4.22E-03) and mmoX gene (9.30E-06) was the highest when copper ion was at 0.03 μmol/L. Finally, we also used MiSeq pyrosequencing to investigate the diversity of microbial community. Methylocystaceae that can co-metabolic degrade TCE were the dominant microorganisms; other microorganisms with the function of direct oxidation of TCE were also included in SWA1 and the microbial diversity decreased significantly along with increasing of copper ion concentration. Based on the above results, variation of copper ion concentration affected the composition of SWA1 and degradation mechanism of TCE. The degradation mechanism of TCE included co-metabolism degradation of methanotrophs and oxidation metabolism directly at copper ion of 0.03 μmol/L. When copper ion at 5 μmol/L (biodegradation was 84.75%), the degradation mechanism of TCE included direct-degradation and co-metabolism degradation of methanotrophs and microorganisms containing phenol hydroxylase. Therefore, biodegradation of TCE by microorganisms was a complicated process, the degradation mechanism included co-metabolism degradation of methanotrophs and bio-oxidation of non-methanotrophs.

Genotoxic potential of copper oxide nanoparticles in the bivalve mollusk Mytilus trossulus

NASA Astrophysics Data System (ADS)

Chelomin, Victor P.; Slobodskova, Valentina V.; Zakhartsev, Maksim; Kukla, Sergey

2017-04-01

Copper oxide nanoparticles (CuO-NPs) are among the most widely used metal oxide nanoparticles, which increases the chance of their being released into the marine environment. As the applications of these particles have increased in recent years, their potential impact on the health of marine biota has also increased. However, the toxicological effects of these NPs in the marine environment are poorly known. In the present study, the DNA damaging potential of CuO-NPs in the marine eastern mussel Mytilus trossulus was evaluated and compared to that of dissolved copper exposures. Genotoxicity was assessed by the single cell gel electrophoresis (comet) assay in mussel gill and digestive gland cells. The results showed that copper in both forms (CuO-NPs and dissolved copper) was accumulated to different extents in mussel tissues. The mussel exposed to the dissolved copper attained higher concentrations of copper in the gills than in the digestive gland. In contrast to these results, it was found that CuO-NPs could induce much higher copper accumulation in the digestive gland than in the gills. A clear and statistically significant increase in DNA damage was found in both tissues of the Cu-exposed group compared to the control mussels. Our results indicated that the CuO-NP exposure produced remarkable effects and increased DNA damage significantly in mussel gill cells only. It should be noted that the digestive gland cells were prone to accumulation following CuO-NPs when compared to the gill cells, while the gill cells were more sensitive to the genotoxic effects of CuO-NPs. These results also suggested the need for a complete risk assessment of engineered particles before its arrival in the consumer market.

Pure and Oxidized Copper Materials as Potential Antimicrobial Surfaces for Spaceflight Activities

NASA Astrophysics Data System (ADS)

Hahn, C.; Hans, M.; Hein, C.; Mancinelli, R. L.; Mücklich, F.; Wirth, R.; Rettberg, P.; Hellweg, C. E.; Moeller, R.

2017-12-01

Microbial biofilms can lead to persistent infections and degrade a variety of materials, and they are notorious for their persistence and resistance to eradication. During long-duration space missions, microbial biofilms present a danger to crew health and spacecraft integrity. The use of antimicrobial surfaces provides an alternative strategy for inhibiting microbial growth and biofilm formation to conventional cleaning procedures and the use of disinfectants. Antimicrobial surfaces contain organic or inorganic compounds, such as antimicrobial peptides or copper and silver, that inhibit microbial growth. The efficacy of wetted oxidized copper layers and pure copper surfaces as antimicrobial agents was tested by applying cultures of Escherichia coli and Staphylococcus cohnii to these metallic surfaces. Stainless steel surfaces were used as non-inhibitory control surfaces. The production of reactive oxygen species and membrane damage increased rapidly within 1 h of exposure on pure copper surfaces, but the effect on cell survival was negligible even after 2 h of exposure. However, longer exposure times of up to 4 h led to a rapid decrease in cell survival, whereby the survival of cells was additionally dependent on the exposed cell density. Finally, the release of metal ions was determined to identify a possible correlation between copper ions in suspension and cell survival. These measurements indicated a steady increase of free copper ions, which were released indirectly by cells presumably through excreted complexing agents. These data indicate that the application of antimicrobial surfaces in spaceflight facilities could improve crew health and mitigate material damage caused by microbial contamination and biofilm formation. Furthermore, the results of this study indicate that cuprous oxide layers were superior to pure copper surfaces related to the antimicrobial effect and that cell density is a significant factor that influences the time dependence of antimicrobial activity.

Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

PubMed

Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

2016-06-01

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental data presented in the two-dimensional plot of hydrogen versus carbon stable isotope signatures.

Copper Oxide Precipitates in NBS Standard Reference Material 482

PubMed Central

Windsor, Eric S.; Carlton, Robert A.; Gillen, Greg; Wight, Scott A.; Bright, David S.

2002-01-01

Copper oxide has been detected in the copper containing alloys of NBS Standard Reference Material (SRM) 482. This occurrence is significant because it represents heterogeneity within a standard reference material that was certified to be homogeneous on a micrometer scale. Oxide occurs as elliptically to spherically shaped precipitates whose size differs with alloy composition. The largest precipitates occur in the Au20-Cu80 alloy and range in size from submicrometer up to 2 μm in diameter. Precipitates are observed using light microscopy, electron microscopy, and secondary ion mass spectrometry (SIMS). SIMS has demonstrated that the precipitates are present within all the SRM 482 wires that contain copper. Only the pure gold wire is precipitate free. Initial results from the analysis of the Au20-Cu80 alloy indicate that the percentage of precipitates is less than 1 % by area. Electron probe microanalysis (EPMA) of large (2 μm) precipitates in this same alloy indicates that precipitates are detectable by EPMA and that their composition differs significantly from the certified alloy composition. The small size and low percentage of these oxide precipitates minimizes the impact that they have upon the intended use of this standard for electron probe microanalysis. Heterogeneity caused by these oxide precipitates may however preclude the use of this standard for automated EPMA analyses and other microanalysis techniques. PMID:27446759

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.

Low temperature synthesis of Ru-Cu alloy nanoparticles with the compositions in the miscibility gap

NASA Astrophysics Data System (ADS)

Martynova, S. A.; Filatov, E. Yu.; Korenev, S. V.; Kuratieva, N. V.; Sheludyakova, L. A.; Plusnin, P. E.; Shubin, Yu. V.; Slavinskaya, E. M.; Boronin, A. I.

2014-04-01

A complex salt [Ru(NH3)5Cl][Cu(C2O4)2H2O]-the precursor of nanoalloys combining ruthenium and copper was prepared. It crystallizes in the monoclinic space group P21/n. Thermal properties of the prepared salt were examined in different atmospheres (helium, hydrogen, oxygen). Thermal decomposition of the precursor in inert atmosphere was thoroughly examined and the intermediate products were characterized. Experimental conditions for preparation of copper-rich (up to 12 at% of copper) metastable solid solution CuxRu1-x (based on Ru structure) were optimized, what is in sharp contrast to the bimetallic miscibility gap known for the bulk counterparts in a wide composition range. Catalytic properties of copper-ruthenium oxide composite were tested in catalytic oxidation of CO.

Friction, wear, and transfer of carbon and graphite to copper, chromium, and aluminum metal surfaces in vacuum

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Sliding friction experiments were conducted with amorphous and fully graphitized carbons sliding on copper and on films of chromium and aluminum on copper. Auger emission spectroscopy analysis was used to monitor carbon transfer to the metal surfaces. Friction and wear were also measured. Metal surfaces were examined both in the clean state and with normal oxides present. Results indicate that different metals have an important effect on friction, wear, and transfer characteristics. With amorphous carbon, the least chemically active metal gave the highest wear and amount of carbon transfer. Both forms of carbon gave lower friction and wear and lower transfer rates when in contact with clean, as opposed to oxide-covered, chromium surfaces. With copper, the reverse was true; cleaning was detrimental.

Copper-promoted methylene C-H oxidation to a ketone derivative by O2.

PubMed

Deville, Claire; McKee, Vickie; McKenzie, Christine J

2017-01-17

The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O 2 in air under ambient conditions when [Cu(dpeo) 2 ](ClO 4 ) 2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO 4 ). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca - ), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca - are not recovered and [Cu(pic) 2 H 2 O] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O 2 activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by H 2 O 2 in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O 2 . The metastable copper complexes [Cu(dpeo) 2 ](ClO 4 ) 2 and [Cu(bpca)(hidpe)](ClO 4 ), along with [NiX 2 (dpeo) 2 ] (X = Cl, Br), [Ni(dpeo) 3 ](ClO 4 ) 2 , [Co(dpeo) 3 ](ClO 4 ) 3 and the mixed valence complex [Fe III Fe(dpeo-H) 3 (dpeo) 3 ](PF 6 ) 4 , have been structurally characterized.

The effects of soil liming and sewage sludge application on dynamics of copper fractions and total copper concentration.

PubMed

Malinowska, Elżbieta

2016-10-01

The paper deals with effects of liming and different doses of municipal sewage sludge (5, 10, and 15 % of soil mass) on copper speciation in soil. In all samples, pH was determined together with total copper concentration, which was measured with the ICP-AES method. Concentration of copper chemical fractions was determined using the seven-step procedure of Zeien and Brümmer. In the soil treated with the highest dose of sludge (15 %), there was, compared to the control, a twofold increase in the concentration of copper and a threefold increase in the concentration of nitrogen. Copper speciation analysis showed that in the municipal sewage sludge the easily soluble and exchangeable fractions (F1 and F2) constituted only a small share of copper with the highest amount of this metal in the organic (F4) and residual (F7) fractions. In the soil, at the beginning of the experiment, the highest share was in the organic fraction (F4), the residual fraction (F7) but also in the fraction where copper is bound to amorphous iron oxides (F5). After 420 days, at the end of the experiment, the highest amount of copper was mainly in the organic fraction (F4) and in the fraction with amorphous iron oxides (F5). Due to mineralization of organic matter in the sewage sludge, copper was released into the soil with the share of the residual fraction (F7) decreasing. In this fraction, there was much more copper in limed soil than in non-limed soil.

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

PubMed

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

2012-01-01

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

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

PubMed Central

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

2012-01-01

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

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

PubMed Central

2015-01-01

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

Isotopically modified nanoparticles for enhanced detection in bioaccumulation studies

USGS Publications Warehouse

Misra, S.K.; Dybowska, A.; Berhanu, D.; Croteau, M.-N.; Luoma, S.N.; Boccaccini, A.R.; Valsami-Jones, E.

2012-01-01

This work presents results on synthesis of isotopically enriched (99% 65Cu) copper oxide nanoparticles and its application in ecotoxicological studies. 65CuO nanoparticles were synthesized as spheres (7 nm) and rods (7 ?? 40 nm). Significant differences were observed between the reactivity and dissolution of spherical and rod shaped nanoparticles. The extreme sensitivity of the stable isotope tracing technique developed in this study allowed determining Cu uptake at exposure concentrations equivalent to background Cu concentrations in freshwater systems (0.2-30 ??g/L). Without a tracer, detection of newly accumulated Cu was impossible, even at exposure concentrations surpassing some of the most contaminated water systems (>1 mg/L). ?? 2011 American Chemical Society.

Graphene Synthesis by Plasma-Enhanced CVD Growth with Ethanol

DOE PAGES

Campo, Teresa; Cotto, María; Márquez, Francisco; ...

2016-03-01

A modified route to synthesize graphene flakes is proposed using the Chemical Vapor Deposition (CVD) technique, by using copper substrates as supports. The carbon source used was ethanol, the synthesis temperature was 950°C and the pressure was controlled along the whole process. In this CVD synthesis process the incorporation of the carbon source was produced at low pressure and 950°C inducing the appearance of a plasma blue flash inside the quartz tube. Apparently, the presence of this plasma blue flash is required for obtaining graphene flakes. The synthesized graphene was characterized by different techniques, showing the presence of non-oxidized graphenemore » with high purity.« less

Nanomolar determination of 4-nitrophenol based on a poly(methylene blue)-modified glassy carbon electrode.

PubMed

Giribabu, Krishnamoorthy; Suresh, Ranganathan; Manigandan, Ramadoss; Munusamy, Settu; Kumar, Sivakumar Praveen; Muthamizh, Selvamani; Narayanan, Vengidusamy

2013-10-07

A poly(methylene blue)-modified glassy carbon electrode (PMB/GCE) was fabricated by electropolymerisation of methylene blue on a GCE and further utilized to investigate the electrochemical determination of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), differential pulse voltammetry and chronocoulometry. The morphology of the PMB on GCE was examined using a scanning electron microscope (SEM). An oxidation peak of 4-NP at the PMB modified electrode was observed at 0.28 V, and in the case of bare GCE, no oxidation peak was observed, which indicates that PMB/GCE exhibits a remarkable effect on the electrochemical determination of 4-NP. Due to this remarkable effect of PMB/GCE, a sensitive and simple electrochemical method was proposed for the determination of 4-NP. The effect of the scan rate and pH was investigated to determine the optimum conditions at which the PMB/GCE exhibits a higher sensitivity with a lower detection limit. Moreover, kinetic parameters such as the electron transfer number, proton transfer number and standard heterogeneous rate constant were calculated. Under optimum conditions, the oxidation current of 4-NP is proportional to its concentration in the range of 15-250 nM with a correlation coefficient of 0.9963. The detection limit was found to be 90 nM (S/N = 3). The proposed method based on PMB/GCE is simple, easy and cost effective. To further confirm its possible application, the proposed method was successfully used for the determination of 4-NP in real water samples with recoveries ranging from 97% to 101.6%. The interference due to sodium, potassium, calcium, magnesium, copper, zinc, iron, sulphate, carbonate, chloride, nitrate and phosphate was found to be almost negligible.

Virgin olive oil blended polyurethane micro/nanofibers ornamented with copper oxide nanocrystals for biomedical applications

PubMed Central

Amna, Touseef; Hassan, M Shamshi; Yang, Jieun; Khil, Myung-Seob; Song, Ki-Duk; Oh, Jae-Don; Hwang, Inho

2014-01-01

Recently, substantial interest has been generated in using electrospun biomimetic nanofibers of hybrids, particularly organic/inorganic, to engineer different tissues. The present work, for the first time, introduced a unique natural and synthetic hybrid micronanofiber wound dressing, composed of virgin olive oil/copper oxide nanocrystals and polyurethane (PU), developed via facile electrospinning. The as-spun organic/inorganic hybrid micronanofibers were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis, X-ray diffraction, electron probe microanalysis, and transmission electron microscopy. The interaction of cells with scaffold was studied by culturing NIH 3T3 fibroblasts on an as-spun hybrid micronanofibrous mat, and viability, proliferation, and growth were assessed. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay results and SEM observation showed that the hybrid micronanofibrous scaffold was noncytotoxic to fibroblast cell culture and was found to benefit cell attachment and proliferation. Hence our results suggest the potential utilization of as-spun micronanoscaffolds for tissue engineering. Copper oxide–olive oil/PU wound dressing may exert its positive beneficial effects at every stage during wound-healing progression, and these micronanofibers may serve diverse biomedical applications, such as tissue regeneration, damaged skin treatment, wound healing applications, etc. Conclusively, the fabricated olive oil–copper oxide/PU micronanofibers combine the benefits of virgin olive oil and copper oxide, and therefore hold great promise for biomedical applications in the near future. PMID:24611006

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

PubMed

Gan, Patrick; Foord, John S; Compton, Richard G

2015-10-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.

Investigation of the storage and release of oxygen in a Cu-Pt element of a high-temperature microcombustor

NASA Astrophysics Data System (ADS)

Khaji, Z.; Sturesson, P.; Hjort, K.; Klintberg, L.; Thornell, G.

2014-11-01

A miniature combustor for converting organic samples into CO2 with application in carbon isotopic measurements has been manufactured and evaluated. The combustor was made of High-Temperature Co-fired Ceramic (HTCC) alumina green tapes. The device has a built-in screen printed heater and a temperature sensor made of platinum, co-sintered with the ceramic. A copper oxide oxygen supply was added to the combustor after sintering by in-situ electroplating of copper on the heater pattern followed by thermal oxidation. Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and Thermal Gravimetric Analysis (TGA) were used to study electroplating, oxidation and the oxide reduction processes. The temperature sensor was calibrated by use of a thermocouple. It demonstrates a temperature coefficient resistance of 4.66×10-3/°C between 32 and 660 °C. The heat characterization was done up to 1000 °C by using IR thermography, and the results were compared with the data from the temperature sensor. Combustion of starch confirmed the feasibility of using copper oxide as the source of oxygen of combustion.

The Activity of Menkes Disease Protein ATP7A Is Essential for Redox Balance in Mitochondria.

PubMed

Bhattacharjee, Ashima; Yang, Haojun; Duffy, Megan; Robinson, Emily; Conrad-Antoville, Arianrhod; Lu, Ya-Wen; Capps, Tony; Braiterman, Lelita; Wolfgang, Michael; Murphy, Michael P; Yi, Ling; Kaler, Stephen G; Lutsenko, Svetlana; Ralle, Martina

2016-08-05

Copper-transporting ATPase ATP7A is essential for mammalian copper homeostasis. Loss of ATP7A activity is associated with fatal Menkes disease and various other pathologies. In cells, ATP7A inactivation disrupts copper transport from the cytosol into the secretory pathway. Using fibroblasts from Menkes disease patients and mouse 3T3-L1 cells with a CRISPR/Cas9-inactivated ATP7A, we demonstrate that ATP7A dysfunction is also damaging to mitochondrial redox balance. In these cells, copper accumulates in nuclei, cytosol, and mitochondria, causing distinct changes in their redox environment. Quantitative imaging of live cells using GRX1-roGFP2 and HyPer sensors reveals highest glutathione oxidation and elevation of H2O2 in mitochondria, whereas the redox environment of nuclei and the cytosol is much less affected. Decreasing the H2O2 levels in mitochondria with MitoQ does not prevent glutathione oxidation; i.e. elevated copper and not H2O2 is a primary cause of glutathione oxidation. Redox misbalance does not significantly affect mitochondrion morphology or the activity of respiratory complex IV but markedly increases cell sensitivity to even mild glutathione depletion, resulting in loss of cell viability. Thus, ATP7A activity protects mitochondria from excessive copper entry, which is deleterious to redox buffers. Mitochondrial redox misbalance could significantly contribute to pathologies associated with ATP7A inactivation in tissues with paradoxical accumulation of copper (i.e. renal epithelia). © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

The Activity of Menkes Disease Protein ATP7A Is Essential for Redox Balance in Mitochondria

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

Bhattacharjee, Ashima; Yang, Haojun; Duffy, Megan

Copper-transporting ATPase ATP7A is essential for mammalian copper homeostasis. Loss of ATP7A activity is associated with fatal Menkes disease and various other pathologies. In cells, ATP7A inactivation disrupts copper transport from the cytosol into the secretory pathway. Using fibroblasts from Menkes disease patients and mouse 3T3-L1 cells with a CRISPR/Cas9-inactivated ATP7A, we demonstrate that ATP7A dysfunction is also damaging to mitochondrial redox balance. In these cells, copper accumulates in nuclei, cytosol, and mitochondria, causing distinct changes in their redox environment. Quantitative imaging of live cells using GRX1-roGFP2 and HyPer sensors reveals highest glutathione oxidation and elevation of H2O2 in mitochondria,more » whereas the redox environment of nuclei and the cytosol is much less affected. Decreasing the H2O2 levels in mitochondria with MitoQ does not prevent glutathione oxidation; i.e. elevated copper and not H2O2 is a primary cause of glutathione oxidation. Redox misbalance does not significantly affect mitochondrion morphology or the activity of respiratory complex IV but markedly increases cell sensitivity to even mild glutathione depletion, resulting in loss of cell viability. Thus, ATP7A activity protects mitochondria from excessive copper entry, which is deleterious to redox buffers. Mitochondrial redox misbalance could significantly contribute to pathologies associated with ATP7A inactivation in tissues with paradoxical accumulation of copper (i.e. renal epithelia).« less

The Activity of Menkes Disease Protein ATP7A Is Essential for Redox Balance in Mitochondria*

PubMed Central

Bhattacharjee, Ashima; Yang, Haojun; Duffy, Megan; Robinson, Emily; Conrad-Antoville, Arianrhod; Lu, Ya-Wen; Capps, Tony; Braiterman, Lelita; Wolfgang, Michael; Murphy, Michael P.; Yi, Ling; Kaler, Stephen G.; Lutsenko, Svetlana; Ralle, Martina

2016-01-01

Copper-transporting ATPase ATP7A is essential for mammalian copper homeostasis. Loss of ATP7A activity is associated with fatal Menkes disease and various other pathologies. In cells, ATP7A inactivation disrupts copper transport from the cytosol into the secretory pathway. Using fibroblasts from Menkes disease patients and mouse 3T3-L1 cells with a CRISPR/Cas9-inactivated ATP7A, we demonstrate that ATP7A dysfunction is also damaging to mitochondrial redox balance. In these cells, copper accumulates in nuclei, cytosol, and mitochondria, causing distinct changes in their redox environment. Quantitative imaging of live cells using GRX1-roGFP2 and HyPer sensors reveals highest glutathione oxidation and elevation of H2O2 in mitochondria, whereas the redox environment of nuclei and the cytosol is much less affected. Decreasing the H2O2 levels in mitochondria with MitoQ does not prevent glutathione oxidation; i.e. elevated copper and not H2O2 is a primary cause of glutathione oxidation. Redox misbalance does not significantly affect mitochondrion morphology or the activity of respiratory complex IV but markedly increases cell sensitivity to even mild glutathione depletion, resulting in loss of cell viability. Thus, ATP7A activity protects mitochondria from excessive copper entry, which is deleterious to redox buffers. Mitochondrial redox misbalance could significantly contribute to pathologies associated with ATP7A inactivation in tissues with paradoxical accumulation of copper (i.e. renal epithelia). PMID:27226607

Oxidative stress, d-ROMs test, and ceruloplasmin.

PubMed

Colombini, Francesco; Carratelli, Mauro; Alberti, Angelo

2016-01-01

Human serum samples were evaluated for oxidative stress with the d-ROMs test. The ceruloplasmin (CP) and copper contents of the samples was independently measured and compared to those calculated on the basis of the d-ROMs test results for pure CP solutions. The d-ROMs readings did not show any significant correlation with either the CP or copper contents of the samples. Critical interference of CP on the d-ROMs test was therefore excluded and the usefulness of the test in the evaluation of global oxidative status of a biological sample could be reassessed.

Chemical constituents of Baeckea frutescens leaves inhibit copper-induced low-density lipoprotein oxidation.

PubMed

Kamiya, Kohei; Satake, Toshiko

2010-04-01

Oxidative modification of LDL plays an important role in the genesis of arteriosclerosis. This study focused on the effects of the leaves of Baeckea frutescens in the prevention of arteriosclerosis. The leaves of B. frutescens have afforded, besides known flavonoid and chromone glycosides, a novel biflavonoid glycoside, characterized as 3-O-alpha-L-rhamnopyranosylmyricetinyl-(I-2'',II-2'')-3-O-alpha-L-rhamnopyranosylmyricetin on the basis of chemical and spectral evidence. This compound exhibited marked inhibition of copper-induced LDL oxidation. Copyright (c) 2009 Elsevier B.V. All rights reserved.

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.

Water Adsorption and Dissociation on Polycrystalline Copper Oxides: Effects of Environmental Contamination and Experimental Protocol

DOE PAGES

Trotochaud, Lena; Head, Ashley R.; Pletincx, Sven; ...

2017-11-02

We use ambient-pressure X-ray photoelectron spectroscopy (APXPS) to study chemical changes, including hydroxylation and water adsorption, at copper oxide surfaces from ultrahigh vacuum to ambient relative humidities of ~5%. Polycrystalline CuO and Cu 2O surfaces were prepared by selective oxidation of metallic copper foils. For both oxides, hydroxylation occurs readily, even at high-vacuum conditions. Hydroxylation on both oxides plateaus near ~0.01% relative humidity (RH) at a coverage of ~1 monolayer. In contrast to previous studies, neither oxide shows significant accumulation of molecular water; rather, both surfaces show a high affinity for adventitious carbon contaminants. Results of isobaric and isothermic experimentsmore » are compared, and the strengths and potential drawbacks of each method are discussed. We also provide critical evaluations of the effects of the hot filament of the ion pressure gauge on the reactivity of gas-phase species, the peak fitting procedure on the quantitative analysis of spectra, and rigorous accounting of carbon contamination on data analysis and interpretation. Lastly, this work underscores the importance of considering experimental design and data analysis protocols during APXPS experiments with water vapor in order to minimize misinterpretations arising from these factors.« less

Water Adsorption and Dissociation on Polycrystalline Copper Oxides: Effects of Environmental Contamination and Experimental Protocol

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

Trotochaud, Lena; Head, Ashley R.; Pletincx, Sven

We use ambient-pressure X-ray photoelectron spectroscopy (APXPS) to study chemical changes, including hydroxylation and water adsorption, at copper oxide surfaces from ultrahigh vacuum to ambient relative humidities of ~5%. Polycrystalline CuO and Cu 2O surfaces were prepared by selective oxidation of metallic copper foils. For both oxides, hydroxylation occurs readily, even at high-vacuum conditions. Hydroxylation on both oxides plateaus near ~0.01% relative humidity (RH) at a coverage of ~1 monolayer. In contrast to previous studies, neither oxide shows significant accumulation of molecular water; rather, both surfaces show a high affinity for adventitious carbon contaminants. Results of isobaric and isothermic experimentsmore » are compared, and the strengths and potential drawbacks of each method are discussed. We also provide critical evaluations of the effects of the hot filament of the ion pressure gauge on the reactivity of gas-phase species, the peak fitting procedure on the quantitative analysis of spectra, and rigorous accounting of carbon contamination on data analysis and interpretation. Lastly, this work underscores the importance of considering experimental design and data analysis protocols during APXPS experiments with water vapor in order to minimize misinterpretations arising from these factors.« less

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation

NASA Astrophysics Data System (ADS)

Hoppe, E. W.; Seifert, A.; Aalseth, C. E.; Bachelor, P. P.; Day, A. R.; Edwards, D. J.; Hossbach, T. W.; Litke, K. E.; McIntyre, J. I.; Miley, H. S.; Schulte, S. M.; Smart, J. E.; Warren, G. A.

2007-08-01

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaning of surfaces. The acidified hydrogen peroxide solution will generally target the Cu +/Cu 2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified.

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

NASA Astrophysics Data System (ADS)

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

2015-02-01

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

Three modified activated carbons by different ligands for the solid phase extraction of copper and lead.

PubMed

Ghaedi, M; Ahmadi, F; Tavakoli, Z; Montazerozohori, M; Khanmohammadi, A; Soylak, M

2008-04-15

In the presented work, 5,5-diphenylimidazolidine-2,4-dione (phenytoin) (DFTD), 5,5-diphenylimidazolidine-2-thione-,4-one (thiophenytoin) (DFID) and 2-(4'-methoxy-benzylidenimine) thiophenole (MBIP) modified activated carbons have been used for the solid phase extraction of copper and lead ions prior to their flame atomic absorption spectrometric determinations. The influences of the various analytical parameters including pH, amounts of reagent, sample volume and eluent type, etc. on the recovery efficiencies of copper and lead ions were investigated. The influences of alkaline, earth alkaline and some transition metals on the adsorption of the analytes were also examined. The detection limits by three sigma for analyte ions were 0.65 and 0.42 microg L(-1) using activated carbon modified with DFID; 0.52 and 0.37 microg L(-1) using activated carbon modified with DFTD and 0.46 and 0.31 microg L(-1) using activated carbon modified with MBIP for Pb(II) and Cu(II), respectively. The procedure was applied to the determination of analytes in natural waters, soil, and blood samples with satisfactory results (recoveries greater than 95%, R.S.D.'s lower than 4%).

Method for providing uranium with a protective copper coating

DOEpatents

Waldrop, Forrest B.; Jones, Edward

1981-01-01

The present invention is directed to a method for providing uranium metal with a protective coating of copper. Uranium metal is subjected to a conventional cleaning operation wherein oxides and other surface contaminants are removed, followed by etching and pickling operations. The copper coating is provided by first electrodepositing a thin and relatively porous flash layer of copper on the uranium in a copper cyanide bath. The resulting copper-layered article is then heated in an air or inert atmosphere to volatilize and drive off the volatile material underlying the copper flash layer. After the heating step an adherent and essentially non-porous layer of copper is electro-deposited on the flash layer of copper to provide an adherent, multi-layer copper coating which is essentially impervious to corrosion by most gases.

Modification of surface properties of copper-refractory metal alloys

DOEpatents

Verhoeven, John D.; Gibson, Edwin D.

1993-10-12

The surface properties of copper-refractory metal (CU-RF) alloy bodies are modified by heat treatments which cause the refractory metal to form a coating on the exterior surfaces of the alloy body. The alloys have a copper matrix with particles or dendrites of the refractory metal dispersed therein, which may be niobium, vanadium, tantalum, chromium, molybdenum, or tungsten. The surface properties of the bodies are changed from those of copper to that of the refractory metal.

Tissue Trace Elements and Lipid Peroxidation in Breeding Female Bank Voles Myodes glareolus.

PubMed

Bonda-Ostaszewska, Elżbieta; Włostowski, Tadeusz; Łaszkiewicz-Tiszczenko, Barbara

2018-04-27

Recent studies have demonstrated that reproduction reduces oxidative damage in various tissues of small mammal females. The present work was designed to determine whether the reduction of oxidative stress in reproductive bank vole females was associated with changes in tissue trace elements (iron, copper, zinc) that play an essential role in the production of reactive oxygen species. Lipid peroxidation (a marker of oxidative stress) and iron concentration in liver, kidneys, and skeletal muscles of reproducing bank vole females that weaned one litter were significantly lower than in non-reproducing females; linear regression analysis confirmed a positive relation between the tissue iron and lipid peroxidation. The concentrations of copper were significantly lower only in skeletal muscles of reproductive females and correlated positively with lipid peroxidation. No changes in tissue zinc were found in breeding females when compared with non-breeding animals. These data indicate that decreases in tissue iron and copper concentrations may be responsible for the reduction of oxidative stress in reproductive bank vole females.

Copper oxide nanowires as better performance electrode material for supercapacitor application

NASA Astrophysics Data System (ADS)

Yar, A.; Dennis, J. O.; Mohamed, N. M.; Mian, M. U.; Irshad, M. I.; Mumtaz, A.

2016-11-01

Supercapacitors are highly attractive energy storage devices which are capable of delivering high power, with fast charging and long cycle life. Carbon based material rely on physical charging with less capacitance while metal oxide store charge by fast redox reaction with increased capacitance. Among metal oxide, copper oxide compounds are widely use in the form of nano and micro structures with no definite control over structure. In this work we utilized the well-controlled structure copper wires, originated from AAO template. Such well controlled structure offer better capacitance values due to easily excess of ions to the surface of wires. Performance of material was check in 3 M of potassium hydroxide (KOH). Specific capacitance (Cs) was calculated by using cyclic voltammetry (CV) and Charge discharge (CDC) test. The capacitance calculate on base on CV at 25 mV/s was 101.37 F/g while CDC showed the capacitance of 90 F/g at 2 A/g.

Near infrared spectroscopy for prediction of antioxidant compounds in the honey.

PubMed

Escuredo, Olga; Seijo, M Carmen; Salvador, Javier; González-Martín, M Inmaculada

2013-12-15

The selection of antioxidant variables in honey is first time considered applying the near infrared (NIR) spectroscopic technique. A total of 60 honey samples were used to develop the calibration models using the modified partial least squares (MPLS) regression method and 15 samples were used for external validation. Calibration models on honey matrix for the estimation of phenols, flavonoids, vitamin C, antioxidant capacity (DPPH), oxidation index and copper using near infrared (NIR) spectroscopy has been satisfactorily obtained. These models were optimised by cross-validation, and the best model was evaluated according to multiple correlation coefficient (RSQ), standard error of cross-validation (SECV), ratio performance deviation (RPD) and root mean standard error (RMSE) in the prediction set. The result of these statistics suggested that the equations developed could be used for rapid determination of antioxidant compounds in honey. This work shows that near infrared spectroscopy can be considered as rapid tool for the nondestructive measurement of antioxidant constitutes as phenols, flavonoids, vitamin C and copper and also the antioxidant capacity in the honey. Copyright © 2013 Elsevier Ltd. All rights reserved.

Formation of nickel and copper ferrites in ceramics: a potential reaction in the reuse of iron-rich sludge incineration ash.

PubMed

Shih, Kaimin

2012-12-01

This study investigates potential solid-state reactions for the stabilization of hazardous metals when reusing the incineration ash from chemically enhanced primary treatment (CEPT) sludge to fabricate ceramic products. Nickel and copper were used as examples of hazardous metals, and the iron content in the reaction system was found to play a major role in incorporating these hazardous metals into their ferrite phases (NiFe2O4 and CuFe2O4). The results from three-hour sintering experiments on NiO + Fe2O3 and CuO + Fe2O3 systems clearly demonstrate the potential for initiating metal incorporation mechanisms using an iron-containing precursor at attainable ceramic sintering temperatures (above 750 degrees C). Both ferrite phases were examined using a prolonged leaching experiment modified from the widely used toxicity characteristic leaching procedure (TCLP) to evaluate their long-term metal leachability. The leaching results indicate that both the NiFe2O4 and the CuFe2O4 products were significantly superior to their oxide forms in immobilizing hazardous metals.

Development of an enzyme free glucose sensor based on copper oxide-graphene composite by using green reducing agent ascorbic acid

NASA Astrophysics Data System (ADS)

Palve, Yogesh Pandit; Jha, Neetu

2018-05-01

In this research work we have developed high sensitive and selective glucose sensor based on copper oxide-graphene composite which is prepared by green synthesis method and used for nonenzymatic glucose sensor. In present paper we report that present method highly selective, simple, efficient, accurate, ecofriendly, less toxic. The prepared composite were characterized by material characterization like SEM, XRD and also by electrochemical characterization like CV, chronoamperometry represents that copper oxide-graphene shows excellent electrocatalytic activity towards glucose, exhibiting a good sensitivity of 103.84 µA mM-1 cm-2, a fast response time 2s, a low detection limit 0.00033µM and linear range from 10 µM-3000 µM. The present sensor can successfully apply for determination of glucose concentration in human blood sample.

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

NASA Astrophysics Data System (ADS)

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

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

Life test results for an ensemble of CO2 lasers

NASA Technical Reports Server (NTRS)

Peruso, C. J.; Degnan, J. J.; Hochuli, U. E.

1978-01-01

The effects of cathode material, cathode operating temperature, anode configuration, window materials, and hydrogen additives on laser lifetime are determined. Internally oxidized copper and silber-copper alloy cathodes were tested. The cathode operating temperature was raised in some tubes through the use of thermal insulation. Lasers incorporating thermally insulated silver copper oxide cathodes clearly yielded the longest lifetimes-typically in excess of 22,000 hours. The use of platinum sheet versus platinum pin anodes had no observable effect on laser lifetime. Similarly, the choice of germanium, cadmium telluride, or zinc selenide as the optical window material appears to have no impact on lifetime.

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

PubMed

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

2017-03-01

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

Bioleaching of copper oxide ore by Pseudomonas aeruginosa

NASA Astrophysics Data System (ADS)

Shabani, M. A.; Irannajad, M.; Azadmehr, A. R.; Meshkini, M.

2013-12-01

Bioleaching is an environmentally friendly method for extraction of metal from ores. In this study, bioleaching of copper oxide ore by Pseudomonas aeruginosa was investigated. Pseudomonas aeruginosa is a heterotrophic bacterium that can produce various organic acids in an appropriate culture medium, and these acids can operate as leaching agents. The parameters, such as particle size, glucose percentage in the culture medium, bioleaching time, and solid/liquid ratio were optimized. Optimum bioleaching conditions were found as follows: particle size of 150-177 μm, glucose percentage of 6%, bioleaching time of 8 d, and solid/liquid ratio of 1:80. Under these conditions, 53% of copper was extracted.

Direct-writing of copper-based micropatterns on polymer substrates using femtosecond laser reduction of copper (II) oxide nanoparticles

NASA Astrophysics Data System (ADS)

Mizoshiri, Mizue; Ito, Yasuaki; Sakurai, Junpei; Hata, Seiichi

2017-04-01

Copper (Cu)-based micropatterns were fabricated on polymer substrates using femtosecond laser reduction of copper (II) oxide (CuO) nanoparticles. CuO nanoparticle solution, which consisted of CuO nanoparticles, ethylene glycol as a reductant agent, and polyvinylpyrrolidone as a dispersant, was spin-coated on poly(dimethylsiloxane) (PDMS) substrates and was irradiated by focused femtosecond laser pulses to fabricate Cu-based micropatterns. When the laser pulses were raster-scanned onto the solution, CuO nanoparticles were reduced and sintered. Cu-rich and copper (I)-oxide (Cu2O)-rich micropatterns were formed at laser scanning speeds of 15 mm/s and 0.5 mm/s, respectively, and at a pulse energy of 0.54 nJ. Cu-rich electrically conductive micropatterns were obtained without significant damages on the substrates. On the other hand, Cu2O-rich micropatterns exhibited no electrical conductivity, indicating that microcracks were generated on the micropatterns by thermal expansion and shrinking of the substrates. We demonstrated a direct-writing of Cu-rich micro-temperature sensors on PDMS substrates using the foregoing laser irradiation condition. The resistance of the fabricated sensors increased with increasing temperature, which is consistent with that of Cu. This direct-writing technique is useful for fabricating Cu-polymer composite microstructures.

Selection of associated heterotrophs by methane-oxidizing bacteria at different copper concentrations.

PubMed

van der Ha, David; Vanwonterghem, Inka; Hoefman, Sven; De Vos, Paul; Boon, Nico

2013-03-01

Due to the increasing atmospheric concentration of the greenhouse gas methane, more knowledge is needed on the management of methanotrophic communities. While most studies have focused on the characteristics of the methane-oxidizing bacteria (MOB), less is known about their interactions with the associated heterotrophs. Interpretative tools based on denaturing gradient gel electrophoresis allowed to evaluate the influence of copper-an important enzymatic regulator for MOB-on the activity and composition of the bacterial community. Over 30 days, enrichments with 0.1, 1.0 and 10 μM Cu(2+) respectively, showed comparable methane oxidation activities. The different copper concentrations did not create major shifts in the methanotrophic communities, as a Methylomonas sp. was able to establish dominance at all different copper concentrations by switching between both known methane monooxygenases. The associated heterotrophic communities showed continuous shifts, but over time all cultures evolved to a comparable composition, independent of the copper concentration. This indicates that the MOB selected for certain heterotrophs, possibly fulfilling vital processes such as removal of toxic compounds. The presence of a large heterotrophic food web indirectly depending on methane as sole carbon and energy source was confirmed by a clone library wherein MOB only formed a minority of the identified species.

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

PubMed Central

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

2016-01-01

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

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

PubMed

Tobisch, Sven

2017-12-14

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

Internal oxidation phenomenon in pure copper

NASA Astrophysics Data System (ADS)

Rudolf, Rebeka; Anžel, Ivan

2009-04-01

This paper presents two special kinds of internal oxidation phenomenon that can take place in pure metals containing a high concentration of non-equilibrium defects. These processes are Internal Oxidation (IO) and Internal Carbonisation (IC). Both processes start with the dissolution of oxidant (O or C) into the pure metal at the free surfaces, and continue with the diffusion of oxidant atoms into the metal matrix volume, where they are trapped at numerous defects within the crystal lattice. Increasing oxidant activity at these places causes local oxidation of the matrix and, consequently, precipitation of fine oxide or graphite particles. The IO and IC processes were tested on the rapidly solidified pure copper which was produced by the Chill-Block Melt Spinning Technique. Analysis of the IO process showed the formation of Cu-Cu2O, and the formation of Cu-C composite from the IC process.

Study on the poisoning effect-of non-vanadium catalysts by potassium

NASA Astrophysics Data System (ADS)

Zeng, Huanmu; Liu, Ying; Yu, Xiaowei; Lin, Yasi

2018-02-01

The poisoning effect of catalyst by alkali metals is one of the problems in the selective catalytic reduction (SCR) of NO by NH3. Serious deactivation by alkali poisoning have been proved to take place in the commercial vanadium catalyst. Recently, non-vanadium catalysts such as copper oxides, manganese oxides, chromium oxides and cerium oxides have attracted special attentions in SCR application. However, their tolerance in the presence of alkali metals is still doubtful. In this paper, copper oxides, manganese oxides, chromium oxides and cerium oxides supported on TiO2 nanoparticle was prepared by impregnating method. Potassium nitrate was chosen as the precursor of poisoner. Catalytic activities of these catalysts were evaluated before and after the addition of potassium. Some characterization methods including X-ray diffraction and temperature programmed desorption was utilized to reveal the main reason of alkali deactivation.

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

PubMed

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

2014-07-25

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

Copper-catalyzed oxidative homo- and cross-coupling of Grignard reagents using diaziridinone.

PubMed

Zhu, Yingguang; Xiong, Tao; Han, Wenyong; Shi, Yian

2014-12-05

Transition-metal-catalyzed cross-coupling reactions are among the most powerful synthetic transformations. This paper describes an efficient copper-catalyzed homo- and cross-coupling of Grignard reagents with di-tert-butyldiaziridinone as oxidant under mild conditions, giving the coupling products in good to excellent yields. The reaction process has a broad substrate scope and is also effective for the C(sp)-C(sp(3)) coupling.

Determination of heavy metals in mussel and oyster samples with tris (2,2‧-bipyridyl) ruthenium (II)/graphene/Nafion® modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

Palisoc, Shirley T.; Uy, Donald Jans S.; Natividad, Michelle T.; Lopez, Toni Beth G.

2017-11-01

Tris (2,2‧-bipyridyl)ruthenium(II)/graphene/Nafion® modified glassy carbon electrodes (GCEs) were fabricated using the drop coating method. The modified electrode was used as the working electrode in differential pulse voltammetry (DPV) for the determination of lead, cadmium, and copper in mussel and oyster samples. The concentration of Tris (2,2‧-bipyridyl) ruthenium (II) and graphene were varied while those of Nafion®, methanol, and ethanol were held constant in the coating solution. The morphology and elemental composition of the fabricated electrodes were analyzed by scanning electron microscopy and energy-dispersive x-ray spectroscopy. Cyclic voltammetry (CV) was done to investigate the reversibility and stability of the modified electrodes. The modified electrode with the best figures of merit was utilized for the detection of copper (Cu2+), lead (Pb2+) and cadmium (Cd2+) via DPV. This was the electrode modified with 4 mg [Ru (bpy)3]2+ and 3 mg graphene. The anodic current and metal concentration showed linear relationship in the range of 48 ppb-745 ppb for Pb2+, 49 ppb-613 ppb for Cd2+, and 28 ppb-472 ppb for Cu2+. The limits of detection for lead, cadmium, and copper were 48 ppb, 49 ppb, and 28 ppb, respectively. Results from atomic absorption spectrometry (AAS) were compared with those measured with DPV. Lead, cadmium, and copper were in mussels, oysters, and sea water. In addition, DPV was able to detect other metals such as zinc, iron, tin and mercury in sea water samples and some samples of oysters.

Acute and sub-lethal exposure to copper oxide nanoparticles causes oxidative stress and teratogenicity in zebrafish embryos.

PubMed

Ganesan, Santhanamari; Anaimalai Thirumurthi, Naveenkumar; Raghunath, Azhwar; Vijayakumar, Savitha; Perumal, Ekambaram

2016-04-01

Nano-copper oxides are a versatile inorganic material. As a result of their versatility, the immense applications and usage end up in the environment causing a concern for the lifespan of various beings. The ambiguities surround globally on the toxic effects of copper oxide nanoparticles (CuO-NPs). Hence, the present study endeavored to study the sub-lethal acute exposure effects on the developing zebrafish embryos. The 48 hpf LC50 value was about 64 ppm. Therefore, we have chosen the sub-lethal dose of 40 and 60 ppm for the study. Accumulation of CuO-NPs was evidenced from the SEM-EDS and AAS analyzes. The alterations in the AChE and Na(+)/K(+)-ATPase activities disrupted the development process. An increment in the levels of oxidants with a concomitant decrease in the antioxidant enzymes confirmed the induction of oxidative stress. Oxidative stress triggered apoptosis in the exposed embryos. Developmental anomalies were observed with CuO-NPs exposure in addition to oxidative stress in the developing embryos. Decreased heart rate and hatching delay hindered the normal developmental processes. Our work has offered valuable data on the connection between oxidative stress and teratogenicity leading to lethality caused by CuO-NPs. A further molecular mechanism unraveling the uncharted connection between oxidative stress and teratogenicity will aid in the safe use of CuO-NPs. Copyright © 2015 John Wiley & Sons, Ltd.

Crystallization of copper metaphosphate glass

NASA Technical Reports Server (NTRS)

Bae, Byeong-Soo; Weinberg, Michael C.

1993-01-01

The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)3),independent of the (Cu sup 2+)/(Cu(total)). However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the (Cu sup 2+)/(Cu (total)) ratio in the glass. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, but small at high temperature. The glass transition temperature of the glass increases as the (Cu sup 2+)/(Cu(total)) ratio is raised. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.

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

PubMed Central

Lucas, Heather R.; Lee, Jennifer C.

2010-01-01

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

Effect of Na4O7P2 on Cu powder preparation from Cu2O-water slurry system.

PubMed

Ahn, J G; Hoang, T H; Kim, D J; Kim, M S; Kim, C O; Chung, H S

2008-03-01

A unique approach is presented for preparing highly dispersed ultrafine copper particles from cuprous oxide slurry using a wet chemical reaction with hydrazine (N2H4) as a reductant along with an appropriate addition of sodium pyrophosphate (Na4O7P2) as a surfactant. It was found that very thin oxidized surfaces on the copper particles are formed during the reaction in the solution and subsequently sodium pyrophosphate plays an important role in the zeta potential of the particles, affecting their dispersion and growth significantly. The copper particles at low zeta potential easily aggregate and grow to bigger ones, whereas they at high zeta potential keep away each other and grew individually to ultrafine size. Additionally, a model for the copper particles growth in accordance with dispersion is proposed.

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

PubMed

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

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

PubMed

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

2017-05-12

Copper oxide nanoparticles (CuO NPs) are being increasingly applied in the industry which results inevitably in the release of these materials into the hydrosphere. In this study, simulated waste-activated sludge experiments were conducted to investigate the effects of Copper Oxide NPs at concentrations of 0.1, 1, 10 and 50 mg/L and to compare it with its ionic counterpart (CuSO 4 ). It was found that 0.1 mg/L of CuO NPs had negligible effects on Chemical Oxygen Demand (COD) and ammonia removal. However, the presence of 1, 10 and 50 mg/L of CuO NPs decreased COD removal from 78.7% to 77%, 52.1% and 39.2%, respectively (P < 0.05). The corresponding effluent ammonium (NH 4 -N) concentration increased from 14.9 mg/L to 18, 25.1 and 30.8 mg/L, respectively. Under equal Cu concentration, copper ions were more toxic towards microorganisms compared to CuO NPs. CuO NPs were removed effectively (72-93.2%) from wastewater due to a greater biosorption capacity of CuO NPs onto activated sludge, compared to the copper ions (55.1-83.4%). The SEM images clearly showed the accumulation and adsorption of CuO NPs onto activated sludge. The decrease in Live/dead ratio after 5 h of exposure of CuO NPs and Cu 2+ indicated the loss of cell viability in sludge flocs.

Ceruloplasmin and cardiovascular disease

NASA Technical Reports Server (NTRS)

Fox, P. L.; Mazumder, B.; Ehrenwald, E.; Mukhopadhyay, C. K.

2000-01-01

Transition metal ion-mediated oxidation is a commonly used model system for studies of the chemical, structural, and functional modifications of low-density lipoprotein (LDL). The physiological relevance of studies using free metal ions is unclear and has led to an exploration of free metal ion-independent mechanisms of oxidation. We and others have investigated the role of human ceruloplasmin (Cp) in oxidative processes because it the principal copper-containing protein in serum. There is an abundance of epidemiological data that suggests that serum Cp may be an important risk factor predicting myocardial infarction and cardiovascular disease. Biochemical studies have shown that Cp is a potent catalyst of LDL oxidation in vitro. The pro-oxidant activity of Cp requires an intact structure, and a single copper atom at the surface of the protein, near His(426), is required for LDL oxidation. Under conditions where inhibitory protein (such as albumin) is present, LDL oxidation by Cp is optimal in the presence of superoxide, which reduces the surface copper atom of Cp. Cultured vascular endothelial and smooth muscle cells also oxidize LDL in the presence of Cp. Superoxide release by these cells is a critical factor regulating the rate of oxidation. Cultured monocytic cells, when activated by zymosan, can oxidize LDL, but these cells are unique in their secretion of Cp. Inhibitor studies using Cp-specific antibodies and antisense oligonucleotides show that Cp is a major contributor to LDL oxidation by these cells. The role of Cp in lipoprotein oxidation and atherosclerotic lesion progression in vivo has not been directly assessed and is an important area for future studies.

[Use of copper oxide wire particles (Copinox) for the prevention of congenital copper deficiency in a herd of German Improved Fawn breed of goat].

PubMed

Winter, P; Hochsteiner, W; Chizzola, R

2004-10-01

In a herd of German Improved Fawn breed of goat in the year 2000 neonatal kid losses due to congenital copper deficiencies were observed. To clarify the problems and to prevent losses in the next breeding season serum copper levels of 10 dams and four control Boer goats were investigated at four time points during one year. Additionally ten kids of the following year were sampled and the serum copper levels were studied. Immediatly after parturition and 8 weeks later the dams showed low serum copper levels (10.4 +/- 11.1 micromol/l, 5.7 +/- 2.9 micromol/l resp.). At the end of the pasture season an increase of serum copper could be measured (19.3 +/- 16.0 micromol/l). To prevent enzootic ataxia due to congenital copper deficiency, the dams were treated with copper oxide wire particles in the next late gestation. At this time point serum copper concentrations started to decrease (18.5 +/- 8.4 micromol/l). The re-examination 3 month later demonstrated an increase of the serum mean copper concentrations up to 23.4 micromol/l in the dams and to 16.2 micromol/l in the kids. The serum copper levels were significantly higher compared to the levels the year before. Big variation of the serum copper levels in the control Boer goats occurred during the year, but no clinical symptoms of copper deficiency could be observed. The copper levels in the grass and soil samples were 6.8 mg/kg and 0.2 mg/kg dry substance, respectively. A secondary copper deficiency based on cadmium could be excluded through the low levels of soil samples. The contents of sulphur and molybdenum were not determined. The results indicate that the German Improved Fawn breed of goats suffered from a primary copper deficiency due to the inefficient mineral supplementation. The administration of Copinox in the last third of the gestation leads to a continious raising of the copper concentrations in the serum and is suited to prevent ataxia due to congential copper deficiency in neonatal kids.

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

Leite, Carlos Eduardo, E-mail: carlos.leite@pucrs.br; Programa de Pós-Graduação em Medicina: Ciências Médicas, Universidade Federal do Rio Grande do Sul, Porto Alegre, CEP 90035-003; Maboni, Lucas de Oliveira

The use of zebrafish (Danio rerio) is increasing as an intermediate preclinical model, to prioritize drug candidates for mammalian testing. As the immune system of the zebrafish is quite similar to that of mammals, models of inflammation are being developed for the screening of new drugs. The characterization of these models is crucial for studies that seek for mechanisms of action and specific pharmacological targets. It is well known that copper is a metal that induces damage and cell migration to hair cells of lateral line of zebrafish. Extracellular nucleotides/nucleosides, as ATP and adenosine (ADO), act as endogenous signaling moleculesmore » during tissue damage by exerting effects on inflammatory and immune responses. The present study aimed to characterize the inflammatory status, and to investigate the involvement of the purinergic system in copper-induced inflammation in zebrafish larvae. Fishes of 7 days post-fertilization were exposed to 10 μM of copper for a period of 24 h. The grade of oxidative stress, inflammatory status, copper uptake, the activity and the gene expression of the enzymes responsible for controlling the levels of nucleotides and adenosine were evaluated. Due to the copper accumulation in zebrafish larvae tissues, the damage and oxidative stress were exacerbated over time, resulting in an inflammatory process involving IL-1β, TNF-α, COX-2 and PGE{sub 2}. Within the purinergic system, the mechanisms that control the ADO levels were the most involved, mainly the reactions performed by the isoenzyme ADA 2. In conclusion, our data shed new lights on the mechanisms related to copper-induced inflammation in zebrafish larvae. - Graphical abstract: This scheme provides a chronological proposition for the biochemical events induced by copper in zebrafish larvae. The dashed line shows the absorption of copper over the exposure time. After 1 h of exposure to copper, the release of PGE{sub 2} occurs, followed by an increase of MPO (as a consequence of neutrophil migration), increased expression of genes involved in inflammatory events (IL-1β and TNF-α) and, reduction of the anti-inflammatory cytokine IL-10 at 4 h. At 24 h, the copper concentration is found highly increased, what is coincident with oxidative stress. Regarding the purinergic system, it is possible to observe an inhibition of ecto-5′-NT and ADA, with the consequent increase of AMP and ADA, respectively, at 24 h. The expression of enzyme-related genes shows a decrease in the expression of ecto-5′-NT and variable expressions of ADA subfamily enzymes. - Highlights: • Copper led to increased oxidative stress, and decreased the antioxidants' defenses. • Copper induced time-related changes of IL-1β, TNF-α, IL-10 and PGE{sub 2} levels. • ADA activity controls the levels of adenosine in copper-induced inflammation. • ADA 2 is the main ADA subfamily involved. • The purinergic system seems to be involved in the resolution of inflammation.« less

Ore microscopy of the Paoli silver-copper deposit, Oklahoma

USGS Publications Warehouse

Thomas, C.A.; Hagni, R.D.; Berendsen, P.

1991-01-01

The Paoli silver-copper deposit is located in south-central Oklahoma, 56 km south-southeast from Norman, Oklahoma. It was mined for high-grade silver-copper near the beginning of this century, and intensive exploratory drilling during the early 1970's delineated unmined portions of the deposit. A collaborative study between the U.S.G.S., the Kansas Geological Survey, and the University of Missouri-Rolla was undertaken to provide new information on the character of red bed copper deposits of the Midcontinent region. The Paoli deposit has been interpreted to occur as a roll-front type of deposit. The silver and copper mineralization occurs within paleochannels in the Permian Wellington Formation. The silver-copper interfaces appear to be controlled by oxidation-reduction interfaces that are marked by grey to red color changes in the host sandstone. Ore microscopic examinations of polished thin sections show that unoxidized ore consists of chalcocite, digenite, chalcopyrite, covellite and pyrite; and oxidized ores are characterized by covellite, bornite, hematite and goethite. In sandstone-hosted ores, chalcocite and digenite replace dolomite and border clastic quartz grains. In siltstone-hosted ores, the copper sulfide grains have varied shapes; most are irregular in shape and 5-25 ??m across, others have euhedral shapes suggestive of pyrite crystal replacements, and some are crudely spherical and are 120-200 ??m across. Chalcopyrite is the predominant copper sulfide at depth. Covellite and malachite replace chalcocite and digenite near the surface. Silver only occurs as native silver; most as irregularly shaped grains 40-80 ??m across, but some as cruciform crystals that are up to 3.5 mm across. The native silver has been deposited after copper sulfides, and locally replaces chalcocite. Surficial nodules of pyrite, malachite and hematite locally are present in outcrops at the oxidation-reduction fronts. Polished sections of the nodules show that malachite forms a cement around quartz sand grains, and brecciated pyrite grains are surrounded by rims of hematite and goethite. Dolomite is the principal sandstone cement. Cathodoluminescence microscopic study of the mineral has shown that it was deposited during seven periods before the copper sulfide mineralization. ?? 1991.

Distribution and mobility of exogenous copper as influenced by aging and components interactions in three Chinese soils.

PubMed

Shi, Hanzhi; Li, Qi; Chen, Wenli; Cai, Peng; Huang, Qiaoyun

2018-04-01

Copper contamination of soils is a global environmental problem. Soil components (organic matter, clay minerals, and microorganisms) and retention time can govern the adsorption, fixation, and distribution of copper. This study evaluated the interaction effects of soil components and aging on the distribution of exogenous copper. Three typical Chinese soils (Ultisol, Alfisol, and Histosol) were collected from Hunan, Henan, and Heilongjiang Provinces. Soils were incubated with rice straw (RS) and engineered bacteria (Pseudomonas putida X4/pIME) in the presence of exogenous copper for 12 months. Sequential extraction was employed to obtain the distribution of Cu species in soils, and the mobility factors of Cu were calculated. The relationships between soil properties and Cu fractions were analyzed with stepwise multiple linear regression. The results show that organic carbon plays a more important role in shaping the distribution of relatively mobile Cu, and iron oxides can be more critical in stabilizing Cu species in soils. Our results suggest that organic matter is the most important factor influencing copper partitioning in Ultisols, while iron oxides are more significant in Alfisols. The mobility of exogenous Cu in soils depends largely on organic carbon, amorphous Fe, and aging. The introduction of both rice straw and rice straw + engineered bacteria enhanced the stabilization of Cu in all the three soils during aging process. The introduction of bacteria could reduce copper mobility, which was indicated by the lowest mobility factors of Cu for the treatment with bacteria in Black, Red, and Cinnamon soils at the first 4, 8, and 8 months, respectively. Different measures should be taken into account regarding the content of organic matter and iron oxides depending on soil types for the risk assessment and remediation of Cu-contaminated soils.

Copper-Catalyzed Oxidative Homo- and Cross-Coupling of Grignard Reagents Using Diaziridinone

PubMed Central

2015-01-01

Transition-metal-catalyzed cross-coupling reactions are among the most powerful synthetic transformations. This paper describes an efficient copper-catalyzed homo- and cross-coupling of Grignard reagents with di-tert-butyldiaziridinone as oxidant under mild conditions, giving the coupling products in good to excellent yields. The reaction process has a broad substrate scope and is also effective for the C(sp)–C(sp3) coupling. PMID:25420218

Copper-catalyzed oxidative C-O bond formation of 2-acyl phenols and 1,3-dicarbonyl compounds with ethers: direct access to phenol esters and enol esters.

PubMed

Park, Jihye; Han, Sang Hoon; Sharma, Satyasheel; Han, Sangil; Shin, Youngmi; Mishra, Neeraj Kumar; Kwak, Jong Hwan; Lee, Cheong Hoon; Lee, Jeongmi; Kim, In Su

2014-05-16

A copper-catalyzed oxidative coupling of 2-carbonyl-substituted phenols and 1,3-dicarbonyl compounds with a wide range of dibenzyl or dialkyl ethers is described. This protocol provides an efficient preparation of phenol esters and enol esters in good yields with high chemoselectivity. This method represents an alternative protocol for classical esterification reactions.

Memristive Responses of Jammed Granular Copper Array Sensors to Mechanical Stress

DTIC Science & Technology

2014-03-27

called Industrial Tectonics Inc. (itiball.com) with the statement of 99.95% minimum copper; stating the residual is most likely silver [12]. Their...atmosphere hot plate and quartz tube furnace with controlled atmosphere were used to oxidize the spheres at various temperatures, the hot plate ...combination spheres, as was seen by Branly. Using a nitric acid etch and 15 minute (min.) hot plate oxidized sphere array consisting of four spheres

Obtention of low oxidation states of copper from Cu 2+-Al 3+ layered double hydroxides containing organic sulfonates in the interlayer

NASA Astrophysics Data System (ADS)

Trujillano, Raquel; Holgado, María Jesús; Rives, Vicente

2009-03-01

A series of hydrotalcite-type compounds containing Cu(II) and Al(III) in the layers, and carbonate or different alkylsulfonates in the interlayer, have been prepared and studied. Calcination of these solids gives rise to formation of metallic copper and Cu 2+ and Cu + oxides or sulfates, depending on the calcination temperature and on the precise nature of the interlayer alkylsulfonate.

Distribution and oxidation state of copper in the cell walls of treated wood examined by synchrotron based XANES and XFM

Treesearch

Samuel L. Zelinka; Grant T. Kirker; Joseph E. Jakes; Leandro Passarini; Barry Lai

2016-01-01

Recently, synchrotron based X-ray fluorescence microscopy (XFM) and X-ray absorption near edge spectroscopy (XANES) were used to examine the metal fastener corrosion in copper-treated wood. XFM is able to map the copper concentration in the wood with a spatial resolution of 0.5 µm and is able to quantify the copper concentration to within 0.05 µg cm-3...

Electronic Structural Analysis of Copper(II)–TEMPO/ABNO Complexes Provides Evidence for Copper(I)–Oxoammonium Character

DOE PAGES

Walroth, Richard C.; Miles, Kelsey C.; Lukens, James T.; ...

2017-09-18

Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and here we probe this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L 2,3- edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-drivenmore » alcohol oxidation reactions, with similar findings. On the whole, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co- catalyst system.« less

Asymptotic Slavery in the Copper Oxide High Temperature Superconductors

NASA Astrophysics Data System (ADS)

Phillips, Philip

2004-05-01

Vast progress in theoretical solid state physics has been made by constructing models which mimic the low-energy properties of solids. Essential to the success of this program is the separability of the high and low energy degrees of freedom. While it is hoped that a high energy reduction can be made to solve the problem of high temperature superconductivity in the copper oxide materials, I will show that no consistent theory is possible if the high energy scale is removed. At the heart of the problem is the mixing of all energy scales (that is, UV-IR mixing) in the copper-oxide materials. Optical experiments demonstrate that the number of low-energy degrees of freedom is derived from a high energy scale. The implications of the inseparability of the high and low energy degrees of freedom on the phase diagram of the cuprates is discussed.

Numerical simulation for aspects of homogeneous and heterogeneous reactions in forced convection flow of nanofluid

NASA Astrophysics Data System (ADS)

Hayat, Tasawar; Shah, Faisal; Khan, Muhammad Ijaz; Alsaedi, Ahmed

2018-03-01

Mixed convection stagnation point flow of nanofluid by a vertical permeable circular cylinder has been addressed. Water is treated as ordinary liquid while nanoparticles include aluminium oxide, copper and titanium dioxide. Homogeneous-heterogeneous reactions are considered. The nonlinear higher order expressions are changed into first ordinary differential equations and then solved by built-in-Shooting method in mathematica. The results of velocity, temperature, concentration, skin friction and local Nusselt number are discussed. Our results demonstrate that surface drag force and heat transfer rate are enhanced linearly for higher estimation of curvature parameter. Further surface drag force decays for aluminium oxide and it enhances for copper nanoparticle. Heat transfer rate enhances with increasing all three types of nanoparticles. In addition, the lowest heat transfer rate is obtained in case of titanium dioxide when compared with copper and aluminium oxide.