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At least 595 records · Page 33

Isolation, characterization, and amino acid sequences of auracyanins, blue copper proteins from the green photosynthetic bacterium Chloroflexus aurantiacus

Three small blue copper proteins designated auracyanin A, auracyanin B-1, and auracyanin B-2 have been isolated from the thermophilic green gliding photosynthetic bacterium Chloroflexus aurantiacus. All three auracyanins are peripheral membrane proteins. Auracyanin A was described previously (Trost, J. T., McManus, J. D., Freeman, J. C., Ramakrishna, B. L., and Blankenship, R. E. (1988) Biochemistry 27, 7858-7863) and is not glycosylated. The two B forms are glycoproteins and have almost identical properties to each other, but are distinct from the A form. The sodium dodecyl sulfate-polyacrylamide gel electrophoresis apparent monomer molecular masses are 14 (A), 18 (B-2), and 22 (B-1) kDa. The amino acid sequences of the B forms are presented. All three proteins have similar absorbance, circular dichroism, and resonance Raman spectra, but the electron spin resonance signals are quite different. Laser flash photolysis kinetic analysis of the reactions of the three forms of auracyanin with lumiflavin and flavin mononucleotide semiquinones indicates that the site of electron transfer is negatively charged and has an accessibility similar to that found in other blue copper proteins. Copper analysis indicates that all three proteins contain 1 mol of copper per mol of protein. All three auracyanins exhibit a midpoint redox potential of +240 mV. Light-induced absorbance changes and electron spin resonance signals suggest that auracyanin A may play a role in photosynthetic electron transfer. Kinetic data indicate that all three proteins can donate electrons to cytochrome c-554, the electron donor to the photosynthetic reaction center.

NASA Discipline Exobiology↗

Electrodeposited copper front metallization for silicon heterojunction solar cells: materials and processes

Even though screen-printing of low-temperature silver paste remains the state-of-the-art technique for the front-metallization of SHJ solar cells, recent studies have demonstrated large efficiency improvements when copper-electroplated contacts are used instead of screen-printed ones. However, due to the new materials and the new processes introduced by this technique, it is crucial to individually investigate their compatibility with the SHJ cell structure. In this study, we present a detailed analysis of how the performances of SHJ devices may be modified by these new materials and processes. First, effects on the amorphous silicon (a-Si:H) passivation have been studied for various processes such as DI water rinsing, dips in a copper removal solution and direct evaporation of copper on the a-Si:H. Finally, copper electroplating technique has been adapted in order to be applied to more complex cell structures such as high-efficiency IBC-SHJ.

Geissbühler, J.↗

Development and Scale-Up of Copper-Based Chemical Looping with Oxygen Uncoupling

The University of Utah has been researching chemical looping with oxygen uncoupling of coal since 2007, focusing on copper-based carriers and a system configuration based on two interconnected circulating fluidized bed reactors. R&D has combined fundamental, lab-scale systems with operation of CLOU reactor systems at various scales and computational simulations for performance evaluation and reactor scale-up. Development has progressed from small lab scale through bench scale with a 10 kW dual bed research reactor to semi-pilot scale with a recently-inaugurated 220 kW chemical looping combustion process development unit. One of the challenges of scaling up copper-based CLOU technology is acquiring enough oxygen carrier material to support operation in larger reactor systems. The UofU CLC PDU, for example, requires 150-200 kg of inventory, so the oxygen carrier must be readily available in large quantities at comparatively low cost. Because no supplier capable of delivering 1+ tons of copper-based oxygen carrier material could be identified, an inexpensive oxygen carrier material was developed in-house and the carrier production process was scaled to produce large quantities of material sufficient for the CLC PDU. This presentation describes development of the CLOU process at the University of Utah, including evaluation of fundamental processes key to performance of CLOU, modeling and scale-up of the process, large-scale production of copper based oxygen carrier material and experience to date with the world’s largest dedicated CLOU reactor.

Whitty, Kevin J.↗

Radiation Induced Corrosion of Copper in Deep Geological Repositories - 19493

This paper presents an overview of the Cu corrosion research being conducted by the Radiation Assisted Materials Performance Science (RAMPS) group at Western University, in collaboration with the Canadian Nuclear Waste Management Organization (NWMO) and Canada Natural Science and Engineering Research Council (NSERC). This paper presents an overview of our research in three areas to develop a high-fidelity copper corrosion model. Copper is an important candidate material for corrosion protection of used nuclear fuel containers (UFC). The UFC and its environment will be exposed to a continuous flux of γ-radiation. The three areas are chemical kinetics of γ-radiolysis of humid air and groundwater, the effects of solution parameters on Cu corrosion dynamics without γ-radiation and the effects of γ-radiation on Cu corrosion dynamics. These studies show that because of the strong feedback loops between processes occurring during copper corrosion, the overall corrosion mechanism may not follow linear dynamics. Presented here are our key findings, their implications for corrosion science in general, and the potential implications of these results for predictions of the adequacy of a UFC copper corrosion allowance. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Fabrication of Copper-Rich Cu-Al Alloy Using the Wire-Arc Additive Manufacturing Process

An innovative wire-arc additive manufacturing (WAAM) process is used to fabricate Cu-9 at. pct Al on pure copper plates in situ, through separate feeding of pure Cu and Al wires into a molten pool, which is generated by the gas tungsten arc welding (GTAW) process. After overcoming several processing problems, such as opening the deposition molten pool on the extremely high-thermal conductive copper plate and conducting the Al wire into the molten pool with low feed speed, the copper-rich Cu-Al alloy was successfully produced with constant predesigned Al content above the dilution-affected area. Also, in order to homogenize the as-fabricated material and improve the mechanical properties, two further homogenization heat treatments at 1073 K (800 °C) and 1173 K (900 °C) were applied. The material and mechanical properties of as-fabricated and heat-treated samples were compared and analyzed in detail. With increased annealing temperatures, the content of precipitate phases decreased and the samples showed gradual improvements in both strength and ductility with little variation in microstructures. The present research opened a gate for in-situ fabrication of Cu-Al alloy with target chemical composition and full density using the additive manufacturing process.

36 MATERIALS SCIENCE↗

Physicochemical Properties of the Molten Iron-Rich Slags Related to the Copper Recovery

The properties of a molten slag play an important role in the separation of the slag from the matte during copper smelting. In this study, the viscosity, electrical conductivity, density, and surface tension of molten FeO{sub t}-SiO{sub 2}-CaO-based slags were measured, and the effects of the common constituents, such as CaO, Fe{sub 3}O{sub 4}, and Cu{sub 2}O, on various properties were investigated. The primary phases in the molten slags which are suitable for the copper recovery process were obtained, and they mainly correspond to fayalite and tridymite. The comparison of the static settling properties of molten industrial copper slag before and after modification is also discussed.

36 MATERIALS SCIENCE↗

Copper fine-structure K-shell electron impact ionization cross sections for fast-electron diagnostic in laser-solid experiments

The K-shell electron impact ionization (EII) cross section, along with the K-shell fluorescence yield, is one of the key atomic parameters for fast-electron diagnostic in laser-solid experiments through the K-shell emission cross section. In addition, copper is a material that has been often used in those experiments because it has a maximum total K-shell emission yield. Furthermore, in a campaign dedicated to the modeling of the K lines of astrophysical interest (Palmeri et al., 2012), the K-shell fluorescence yields for the K-vacancy fine-structure atomic levels of all the copper isonuclear ions have been calculated. In this study, the K-shell EII cross sections connecting the ground and the metastable levels of the parent copper ions to the daughter ions K-vacancy levels considered in Palmeri et al. (2012) have been determined. The relativistic distorted-wave (DW) approximation implemented in the FAC atomic code has been used for the incident electron kinetic energies up to 10 times the K-shell threshold energies. Moreover, the resulting DW cross sections have been extrapolated at higher energies using the asymptotic form proposed by Davies et al. (2013)

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

An unusual 3D interdigitated architecture assembled from Keggin polyoxometalates and dinuclear copper(II) complexes

A novel organic-inorganic hybrid compound, [Cu{sub 2}(bipy){sub 3}({mu}{sub 1}-H{sub 2}O){sub 2}({mu}{sub 2}-H{sub 2}O)({mu}{sub 2}-OH)(H{sub 2}BW{sub 12}O{sub 40})]{center_dot}4 H{sub 2}O (1) (bipy=4,4 Prime -bipy), has been synthesized in hydrothermal condition and characterized by elemental analysis, IR spectrum, TG analysis and single-crystal X-ray diffraction. Compound 1 possesses poly-pendant layered motifs composed of 12-tungstoborates and dinuclear copper(II) complexes, in which the mono-coordinated bipy molecules are orderly appended to both sides of the layer, respectively. Adjacent layers mutually engage in a zipper-like pattern to result in a novel 3D interdigitated architecture. The variable-temperature magnetic susceptibility of 1 showed that there existed weak antiferromagnetic interaction in 1. Toward the reduction of hydrogen peroxide, 1 has good electrocatalytic activity and remarkable stability. - A new compound has been obtained, which represents the first interdigitated architecture assembled by POMs and dinuclear copper(II) complexes. Highlights: Black-Right-Pointing-Pointer The first example of interdigitated architecture assembled by POMs and dinuclear copper(II) complexes is observed. Black-Right-Pointing-Pointer A zipper-like pattern is observed in the structure. Black-Right-Pointing-Pointer The IR, TG, XRPD, magnetism and electrochemical property of the title compound were studied.

36 MATERIALS SCIENCE↗

A new carboxyl-copper-organic framework and its excellent selective absorbability for proteins

One-pot solvothermal treatments of CuCl{sub 2}·2H{sub 2}O, H{sub 2}L (5-(3-methyl-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-yl) isophthalic acid) and Sm(NO{sub 3}){sub 3}·6H{sub 2}O in water yielded a rare carboxyl-copper-organic framework, [Cu(HL)]{sub n}·nH{sub 2}O (1). The existence of carboxyl groups in compound 1 may be due to the interference of Sm(NO{sub 3}){sub 3}·6H{sub 2}O at the relatively high temperature and autogenous pressure of the reaction. Compound 1 has been characterized by single-crystal X-ray diffraction, PXRD, IR, and elemental analysis. Compound 1 is a 3D coordination polymer, and an xfe-4-Fddd, (4{sup 2}.6.8{sup 3}) topology in 1 is created. In addition, the optical properties have been investigated. Rhodamine B dyeing experiments exhibited that there were residual carboxyl groups on the surface of compound 1. UV–vis results showed that more lysozyme was adsorbed onto the surface of compound 1 than BSA at pH 7.4. At the same time, XPS spectra were also investigated to verify the results. - Graphical abstract: One-pot solvothermal treatments of CuCl{sub 2}·2H{sub 2}O, H2L (5-(3-methyl-5-(pyridin-4-yl)-4H-1, 2, 4-triazol-4-yl) isophthalic acid) and Sm(NO{sub 3}){sub 3}·6H{sub 2}O in water yielded a rare carboxyl-copper-organic framework, [Cu(HL)]n·nH{sub 2}O (1). The existence of carboxyl groups in compound 1 may be due to the interference of Sm(NO{sub 3}){sub 3}·6H{sub 2}O at the relatively high temperature and autogenous pressure of the reaction. Compound 1 has been characterized by single-crystal X-ray diffraction, XRPD, IR, and elemental analysis. Compound 1 is a 3D coordination polymer, and an xfe-4-Fddd, (4{sup 2}.6.8{sup 3}) topology in 1 is created. In addition, the optical properties have been investigated. Rhodamine B dyeing experiments exhibited that there were residual carboxyl groups on the surface of compound 1. UV-vis results showed that more lysozyme was adsorbed onto the surface of compound 1 than that of BSA at pH 7.4. At the same time, XPS spectra were also investigated to verify the results. - Highlights: • A rare carboxyl-copper-organic framework has been hydrothermally synthesized. • An xfe-4-Fddd, (4{sup 2}.6.8{sup 3}) topology in 1 is created. • BSA was significantly less adsorbed onto the carboxylic acid-rich surface than lysozyme. • XPS spectra were also investigated to verify the results of protein adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new coordination mode of (E)-3-(3-hydroxyl-phenyl)-acrylic acid in copper complex: Crystal structure and magnetic properties

A copper complex ([Cu(py){sub 2}(L){sub 2}]·2CH{sub 3}OH){sub n} (HL=(E)-3-(3-hydroxyl-phenyl)-acrylic acid) (1) with acrylic acid ligand was synthesized and structurally analyzed by IR, elemental analysis, TGA and the single-crystal X-ray diffraction methods. It is the first time to find that phenolic hydroxyl of L coordinates to Cu(II). Complex 1 exhibits 1D chain by a double-bridge of ligands, and the 3D supramolecular framework in complex 1 is constructed by π–π stacking interactions and van der Waals Contacts among the 1D chains. The magnetic properties of complex 1 have been studied. - Graphical abstract: A copper complex based on (E)-3-(3-hydroxyl-phenyl)-acrylic acid in a novel coordinated way was synthesized and a ferromagnetic exchange interactions between neighboring Cu(II) ions has be achieved. - Highlights: • A new copper complex with acrylic acid ligand was synthesized and analyzed. • We find the phenolic hydroxyl of MCA ligand coordinates to metal ion firstly. • A ferromagnetic exchange interactions between Cu(II) ions has been achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrothermal synthesis and crystal structure of a new lithium copper bismuth oxide, LiCuBiO{sub 4}

A new lithium copper bismuth oxide, LiCuBiO{sub 4} was prepared by hydrothermal reaction using NaBiO{sub 3}0.1*4H{sub 2}O. The crystal structural model of this compound was refined by using synchrotron X-ray powder diffraction data. This bismuthate has the LiCuSbO{sub 4} related structure with the orthorhombic cell (Space group: Pnma) of a=10.9096(9), b=5.8113(5) and c=5.0073(4) Å, and the final R-factors were R{sub wp}=4.84 and R{sub p}=3.58%. This compound is the first example of a lithium copper bismuthate containing Bi{sup 5+}. An antiferromagnetic ordering of Cu{sup 2+} moment was observed at 6 K. - Graphical abstract: In the crystal structure of LiCuBiO{sub 4} all metal atoms are coordinated octahedrally by six O atoms and LiO{sub 6} and CuO{sub 6} octahedra form the one-dimensional chains by edge-sharing along the b-axis. The LiO{sub 6} and CuO{sub 6} chains form the layer by face-sharing in the bc plane. The Bi atoms are placed in that interlayer and BiO{sub 6} octahedra are edge-sharing with LiO{sub 6} and CuO{sub 6} octahedra. - Highlights: • A new lithium copper bismuth oxide, LiCuBiO{sub 4} is prepared by hydrothermal reaction. • The crystal structure of LiCuBiO{sub 4} is closely related with that of LiCuSbO{sub 4}. • This new compound exhibits an antiferromagnetic ordering of Cu{sup 2+} moment at 6 K.

36 MATERIALS SCIENCE↗

Patterned electrochemical deposition of copper using an electron beam

We describe a technique for patterning clusters of metal using electrochemical deposition. By operating an electrochemical cell in the transmission electron microscope, we deposit Cu on Au under potentiostatic conditions. For acidified copper sulphate electrolytes, nucleation occurs uniformly over the electrode. However, when chloride ions are added there is a range of applied potentials over which nucleation occurs only in areas irradiated by the electron beam. By scanning the beam we control nucleation to form patterns of deposited copper. We discuss the mechanism for this effect in terms of electron beam-induced reactions with copper chloride, and consider possible applications.

36 MATERIALS SCIENCE↗

Copper doping of ZnO crystals by transmutation of {sup 64}Zn to {sup 65}Cu: An electron paramagnetic resonance and gamma spectroscopy study

Transmutation of {sup 64}Zn to {sup 65}Cu has been observed in a ZnO crystal irradiated with neutrons. The crystal was characterized with electron paramagnetic resonance (EPR) before and after the irradiation and with gamma spectroscopy after the irradiation. Major features in the gamma spectrum of the neutron-irradiated crystal included the primary 1115.5 keV gamma ray from the {sup 65}Zn decay and the positron annihilation peak at 511 keV. Their presence confirmed the successful transmutation of {sup 64}Zn nuclei to {sup 65}Cu. Additional direct evidence for transmutation was obtained from the EPR of Cu{sup 2+} ions (where {sup 63}Cu and {sup 65}Cu hyperfine lines are easily resolved). A spectrum from isolated Cu{sup 2+} (3d{sup 9}) ions acquired after the neutron irradiation showed only hyperfine lines from {sup 65}Cu nuclei. The absence of {sup 63}Cu lines in this Cu{sup 2+} spectrum left no doubt that the observed {sup 65}Cu signals were due to transmuted {sup 65}Cu nuclei created as a result of the neutron irradiation. Small concentrations of copper, in the form of Cu{sup +}-H complexes, were inadvertently present in our as-grown ZnO crystal. These Cu{sup +}-H complexes are not affected by the neutron irradiation, but they dissociate when a crystal is heated to 900 °C. This behavior allowed EPR to distinguish between the copper initially in the crystal and the copper subsequently produced by the neutron irradiation. In addition to transmutation, a second major effect of the neutron irradiation was the formation of zinc and oxygen vacancies by displacement. These vacancies were observed with EPR.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Uniform surface growth of copper oxide nanowires in radiofrequency plasma discharge and limiting factors

The uniform growth of copper oxide nanowires on the top of copper plate has been investigated during the exposure to radiofrequency plasma discharge in respect to plasma properties and its localization. The copper samples of 10 mm radius and 1 mm in thickness were exposed to argon-oxygen plasma created at discharge power of 150 W. After 10 min, almost uniform growth of nanowires was achieved over large surface. There were significant distortions in nanowire length and shape near the edges. Based on the experimental results, we developed a theoretical model, which took into account a balance in heat released at the flow of the current to the nanowire and rejected from the nanowire. This model established a dependence of the maximal length of the nanowire at dependence on the plasma parameters, where the limiting factor for nanowire growth and distortions in distribution are ballistic effects of ions and their local fluxes. In contrast, the plasma heating by potential interactions of species has very little influence on the length and smaller deviations in flux are allowed for uniformity of growth.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

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

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%.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Growth dynamics of copper oxide nanowires in plasma at low pressures

The growth time dynamics of the copper oxide nanowires (NWs) in radiofrequency plasma discharge were investigated. Grounded copper samples were treated in argon-oxygen plasma with the discharge power of 150 W for sequenced times up to 20 min. After the treatment, the samples were analysed with scanning electron microscopy and image processing to obtain the length and aspect ratio of the NWs. A growth mode with the saturation was observed in dependence to NW length, where the maximal length of 5 μm was achieved in 20 min. However, the best NW aspect ratio had maximum of about 40 after 10 min of plasma treatment. To describe and understand nanowire growth mechanism, a theoretical model was developed and it is in agreement with the experiment. The model results indicate that different densities of the ion current to the side and top area of NW modify the NW growth in height and width. The NW growth is enhanced by presence of ions, and thus this implies that it can be controlled by discharge power. This explains much faster growth of copper oxide nanowires in plasma environment compared to prolonged thermal treatments.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Unusual behavior in magnesium-copper cluster matter produced by helium droplet mediated deposition

We demonstrate the ability to produce core-shell nanoclusters of materials that typically undergo intermetallic reactions using helium droplet mediated deposition. Composite structures of magnesium and copper were produced by sequential condensation of metal vapors inside the 0.4 K helium droplet baths and then gently deposited onto a substrate for analysis. Upon deposition, the individual clusters, with diameters ∼5 nm, form a cluster material which was subsequently characterized using scanning and transmission electron microscopies. Results of this analysis reveal the following about the deposited cluster material: it is in the un-alloyed chemical state, it maintains a stable core-shell 5 nm structure at sub-monolayer quantities, and it aggregates into unreacted structures of ∼75 nm during further deposition. Surprisingly, high angle annular dark field scanning transmission electron microscopy images revealed that the copper appears to displace the magnesium at the core of the composite cluster despite magnesium being the initially condensed species within the droplet. This phenomenon was studied further using preliminary density functional theory which revealed that copper atoms, when added sequentially to magnesium clusters, penetrate into the magnesium cores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of sputtering power on properties of copper oxides thin films deposited on glass substrates

Copper oxides are deposited by radio frequency sputtering using copper target in the mixture of argon and oxygen gasses. The structural and optical properties of the copper oxides deposited at different sputtering powers have been investigated. All the films are single phase polycrystalline. At low RF power (100 W), the film is monoclinic structure of cupric oxide (CuO). Meanwhile, the films are cubic structure of cuprous oxide (Cu2O) at higher RF power. Field emission scanning electron microscopy images show the films have different morphologies with small grain size and consist of a lot of voids. The analysis of energy dispersive X-ray spectroscopy shows that the ratio of Cu to O is increased as the RF power increased. From the ultraviolet–visible spectroscopy, the films have a broad absorption edge in the range of 300–500 nm. The band gap of the films grown at RF power of 100 W, and 120 W and above, were 1.18 eV and 2.16 eV, respectively.

36 MATERIALS SCIENCE↗