Showing papers on "Copper published in 2004"

Ultrahigh strength and high electrical conductivity in copper

Abstract: Methods used to strengthen metals generally also cause a pronounced decrease in electrical conductivity, so that a tradeoff must be made between conductivity and mechanical strength. We synthesized pure copper samples with a high density of nanoscale growth twins. They showed a tensile strength about 10 times higher than that of conventional coarse-grained copper, while retaining an electrical conductivity comparable to that of pure copper. The ultrahigh strength originates from the effective blockage of dislocation motion by numerous coherent twin boundaries that possess an extremely low electrical resistivity, which is not the case for other types of grain boundaries.

Electronic Structures of Metal Sites in Proteins and Models: Contributions to Function in Blue Copper Proteins

Abstract: Approximately one-half of all known protein crystal structures in the protein data bank (PDB) contain metal ion cofactors, which play vital roles in charge neutralization, structure, and function.1,2 These proteins range in size from 5000-107 Da with the metal ion corresponding to only on the order of 0.1 wt % of the molecule. Yet, for a wide range of these metalloproteins, the metal ion and its environment are key to the chemistry as these comprise the active site in catalysis. It is the purpose of this review to present the information content of spectroscopic methods, which allow one to focus in on the metalloactive site (Figure 1), define its electronic structure, evaluate the role of the protein in determining geometric and electronic structure, and elucidate the contributions of electronic structure to function. Metalloproteins are simply metal complexes but with remarkably intricate and complex ligands. The metal ion, clusters of metal ions bridged by oxide or sulfide ligands or equatorially chelated by N-heterocyclic ligands (heme, corrin, etc.), are bound to the protein through one or more of the endogenous ligand lone pair donors in Table 1. Note that for most of the donor groups, this requires deprotonation, and the metal ion competition with the proton for the free base lowers the effective pKA by at least several log units from those intrinsic values listed in Table 1. It is important to emphasize that for a number of the ligands in Tables 1 and 2, in particular phenolate, thiolate, oxo and sulfido, and the N-heterocyclic chelates, the metal complex exhibits extremely intense low energy charge transfer (CT) absorption bands, which reflect highly covalent ligand-metal bonds. These make major contributions to the electronic structure of an active site and can be affected by the geometry of the metal site and the orientation of the ligand-metal bond, which in turn can be influenced by the protein matrix. * To whom correspondence should be addressed. † Department of Chemistry, Stanford University. ‡ Stanford Synchrotron Radiation Laboratory, SLAC, Stanford University. 419 Chem. Rev. 2004, 104, 419−458

High Lithium Metal Cycling Efficiency in a Room-Temperature Ionic Liquid

Abstract: A room-temperature ionic liquid (RTIL) solvent, N-methyl, N-alkyl pyrrolidinium bis(trifluoromethanesulfonyl)amide (P 1 X (Tf) 2 N), has been investigated for use in a lithium metal battery. An average cycling efficiency of>99% is achieved at 1.0 mA cm - 2 (I d e p = I d i s s ) on platinum. At deposition rates up to 1.75 mA cm - 2 optical micrographs indicate that the deposit is uniform and nondendritic. Above 1.75 mA cm - 2 , the deposit becomes dendritic and efficiency decays. High cycling efficiency (>99%) can also be obtained on copper, but at relatively low current density (0.1 mA cm - 2 ). The deposition/cycling history also influences the cycling behavior of the deposit.

Click chemistry in materials synthesis. 1. Adhesive polymers from copper‐catalyzed azide‐alkyne cycloaddition

Abstract: The copper(I)-catalyzed cycloaddition reaction between azides and alkynes has been employed to make metal-adhesive materials. Copper and brass surfaces supply the necessary catalytic Cu ions, and thus the polymerization process occurs selectively on these metals in the absence of added catalysts. Alternatively, copper compounds can be added to monomer mixtures and then introduced to reducing metal surfaces such as zinc to initiate polymerization. The resulting materials were found to possess comparable or superior adhesive strength to standard commercial glues, and structure-activity correlations have identified several important properties of the monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4392–4403, 2004

Deformation twinning in nanocrystalline copper at room temperature and low strain rate

Abstract: The grain-size effect on deformation twinning in nanocrystalline copper is studied. It has been reported that deformation twinning in coarse-grained copper occurs only under high strain rate and/or low-temperature conditions. Furthermore, reducing grain sizes has been shown to suppress deformation twinning. Here, we show that twinning becomes a major deformation mechanism in nanocrystalline copper during high-pressure torsion under a very slow strain rate and at room temperature. High-resolution transmission electron microscopy investigation of the twinning morphology suggests that many twins and stacking faults in nanocrystalline copper were formed through partial dislocation emissions from grain boundaries. This mechanism differs from the pole mechanism operating in coarse-grained copper.

Investigation of the mending effect and mechanism of copper nano-particles on a tribologically stressed surface

Abstract: The mending effect and mechanism of metal nano-particles in an area undergoing wear are quite important for both the fundamental theory of nano-tribology and the development of lubricant additives. This paper presents research on the mending effect of copper nano-particles added to lubricant oil. Pin-on-disk experiments and Scanning Electron Microscopy (SEM) observations show that copper nano-particles do display an excellent mending effect. The observation by Scanning Tunnelling Microscopy (STM) reveals that the mending effect results from the deposition of copper nano-particles onto the wear scar. It has also been disclosed by heating simulation that, due to nano-scale effects, which bring about decrease in the diffusion temperature of copper nano-particles, the heat generated by friction leads to the diffusion of copper nano-particles and their subsequent deposition, which finally results in the so-called mending effect.

Acid/Base-Treated Activated Carbons: Characterization of Functional Groups and Metal Adsorptive Properties

Abstract: Surface modification of activated carbons by various physicochemical methods directs an attractive approach for improvement of heavy metal uptake from aqueous solutions. Activated carbons were modified with HCl and HNO3 optionally followed by NaOH. The effects of surface modifications on the properties of the carbons were studied by the specific surface area, carbon pH, and total acidity capacity as well as by scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The modifications bring about substantial variation in the chemical properties whereas the physical properties remain nearly unchanged. NaOH causes an increase in the content of hydroxyl groups, while the HCl treatment results in an increase in the amount of single-bonded oxygen functional groups such as phenols, ethers, and lactones. The HNO3 modification generates a large number of surface functional groups such as carbonyl, carboxyl, and nitrate groups. The HNO3 modification significantly increases the copper adsorption, while the HCl treatment slightly reduces the copper uptake. Most of the copper ions are adsorbed rapidly in the first 2 h; the adsorption equilibrium is established in around 8 h. An intraparticle diffusion model successfully describes the kinetics of copper adsorption onto the carbons.

Fragmentation of nanowires driven by Rayleigh instability

Abstract: Rayleigh instability of copper nanowires has been experimentally demonstrated. After annealing 30–50-nm-diam wires at temperatures between 400 and 600°C, different stages of the fragmentation process are observed by scanning electron microscopy. At 400°C, the wires start to fragment, forming shorter sections at 500°C, and finally decaying into a chain of nanospheres at 600°C. Average diameter and spacing of the spheres are in agreement with theoretical predictions. The Rayleigh instability applied to nanowires provides a structuring technique producing long chains of nanospheres, which should find interesting applications, for instance, by guiding light below the diffraction limit via coherent coupling of surface-plasmon polaritons.

Room Temperature Aerobic Copper–Catalysed Selective Oxidation of Primary Alcohols to Aldehydes

Abstract: A novel and very mild method for the oxidation of primary alcohols to aldehydes with excellent conversions has been developed. The reaction is carried out under air at room temperature and is catalysed using a [copper(II)-(N ligand)n] complex with TEMPO and a base as co-catalysts. In this paper, the performance of a series of N-containing ligands, as well as different copper(II) salt precursors in different solvents are reported. Best results are obtained in acetonitrile/water as solvent using a copper(II) catalyst generated in situ from a Cu(II) salt with weak or non-coordinating anions and bipyridine ligands with electron-donating substituents. A reaction mechanism is postulated which resembles that of galactose oxidase, and in which TEMPO seems to be involved as a hydrogen acceptor.

Methanobactin, a Copper-Acquisition Compound from Methane-Oxidizing Bacteria

Abstract: Siderophores are extracellular iron-binding compounds that mediate iron transport into many cells. We present evidence of analogous molecules for copper transport from methane-oxidizing bacteria, represented here by a small fluorescent chromopeptide (C45N12O14H62Cu, 1216 daltons) produced by Methylosinus trichosporium OB3b. The crystal structure of this compound, methanobactin, was resolved to 1.15 angstroms. It is composed of a tetrapeptide, a tripeptide, and several unusual moieties, including two 4-thionyl-5-hydroxy-imidazole chromophores that coordinate the copper, a pyrrolidine that confers a bend in the overall chain, and an amino-terminal isopropylester group. The copper coordination environment includes a dual nitrogen- and sulfur-donating system derived from the thionyl imidazolate moieties. Structural elucidation of this molecule has broad implications in terms of organo-copper chemistry, biological methane oxidation, and global carbon cycling.

Intracellular Copper Transport in Mammals

Abstract: Copper is an essential cofactor for approximately a dozen cuproenzymes in which copper is bound to specific amino acid residues in an active site. However, free cuprous ions react readily with hydrogen peroxide to yield the deleterious hydroxyl radical. Therefore, copper homeostasis is regulated very tightly, and unbound copper is extremely low in concentration. Copper imported by the plasma membrane transport protein Ctr1 rapidly binds to intracellular copper chaperone proteins. Atox1 delivers copper to the secretory pathway and docks with either copper-transporting ATPase ATP7B in the liver or ATP7A in other cells. ATP7B directs copper to plasma ceruloplasmin or to biliary excretion in concert with a newly discovered chaperone, Murr1, the protein missing in canine copper toxicosis. ATP7A directs copper within the transgolgi network to the proteins dopamine beta-monooxgenase, peptidylglycine alpha-amidating monooxygenase, lysyl oxidase, and tyrosinase, depending on the cell type. CCS is the copper chaperone for Cu,Zn-superoxide dismutase; it delivers copper in the cytoplasm and intermitochondrial space. Cox17 delivers copper to mitochondria to cytochrome c oxidase via the chaperones Cox11, Sco1, and Sco2. Other copper chaperones may exist and might include metallothionein and amyloid precursor protein (APP). Genetic and nutritional studies have illustrated the essential nature of these copper-binding proteins; alterations in their levels are associated with severe pathology.

Binary Cu–Zr Bulk Metallic Glasses

Abstract: We report that bulk metallic glasses (BMGs) can be produced up to 2 mm by a copper mould casting in CuxZr1−x binary alloy with a wide glass forming composition range (45