Energy distributions of copper ions and atoms sputtered by atomic and molecular ions

Non-resonant multiphoton ionization combined with quadrupole and time-of-flight analysis has been used to study sputtering by both atomic and molecular ion beams. The mass spectra and energy distributions of both sputtered atoms and secondary ions produced by 3.6 keV Ar+, N+, N-2(+), CF2+ and CF3+ ion bombardment at 45 degrees to a polycrystalline copper target have been measured. The energy distributions of the copper ions and atoms are found to be different and quite complex. The ion distributions can generally be described by a linear collision cascade model, with possible evidence for a knock-on contribution. The sputtered atom distributions are partially described by a combination of linear collision cascade and dense cascade (thermal spike) models. This is interpreted as support for a time-evolving sputtering mechanism.

Age-Associated Changes of Brain Copper, Iron, and Zinc in Alzheimer's Disease and Dementia with Lewy Bodies

Disease-, age-, and gender-associated changes in brain copper, iron, and zinc were assessed in postmortem neocortical tissue (Brodmann area 7) from patients with moderate Alzheimer's disease (AD) (n = 14), severe AD (n = 28), dementia with Lewy bodies (n = 15), and normal age-matched control subjects (n = 26). Copper was lower (20%; p < 0.001) and iron higher (10–16%; p < 0.001) in severe AD compared with controls. Intriguingly significant Group*Age interactions were observed for both copper and iron, suggesting gradual age-associated decline of these metals in healthy non-cognitively impaired individuals. Zinc was unaffected in any disease pathologies and no age-associated changes were apparent. Age-associated changes in brain elements warrant further investigation.

Genome Wide Association Mapping of Grain Arsenic, Copper, Molybdenum and Zinc in Rice (Oryza sativa L.) Grown at Four International Field Sites

The mineral concentrations in cereals are important for human health, especially for individuals who consume a cereal subsistence diet. A number of elements, such as zinc, are required within the diet, while some elements are toxic to humans, for example arsenic. In this study we carry out genome-wide association (GWA) mapping of grain concentrations of arsenic, copper, molybdenum and zinc in brown rice using an established rice diversity panel of,300 accessions and 36.9 k single nucleotide polymorphisms (SNPs). The study was performed across five environments: one field site in Bangladesh, one in China and two in the US, with one of the US sites repeated over two years. GWA mapping on the whole dataset and on separate subpopulations of rice revealed a large number of loci significantly associated with variation in grain arsenic, copper, molybdenum and zinc. Seventeen of these loci were detected in data obtained from grain cultivated in more than one field location, and six co-localise with previously identified quantitative trait loci. Additionally, a number of candidate genes for the uptake or transport of these elements were located near significantly associated SNPs (within 200 kb, the estimated global linkage disequilibrium previously employed in this rice panel). This analysis highlights a number of genomic regions and candidate genes for further analysis as well as the challenges faced when mapping environmentally-variable traits in a highly genetically structured diversity panel.

Efficient heterogeneous asymmetric catalysis of the Mukaiyama aldol reaction by silica- and ionic liquid-supported Lewis acid copper(II) complexes of bis(oxazolines)

Lewis acid complexes based on copper(II) and an imidazolium-tagged bis(oxazoline) have been used to catalyse the asymmetric Mukaiyama aldol reaction between methyl pyruvate and 1-methoxy-1-tri-methylsilyloxypropene under homogeneous and heterogeneous conditions. Although the ees obtained in ionic liquid were similar to those found in dichloromethane, there was a significant rate enhancement in the ionic liquid with reactions typically reaching completion within 2 min compared with only 55% conversion after 60 min in dichloromethane. However, this rate enhancement was offset by lower chemoselectivity in ionic liquids due to the formation of 3-hydroxy-1,3-diphenylbutan-1-one as a by-product. Supporting the catalyst on silica or an imidazolium-modified silica using the ionic liquid or in an ionic liquid-diethyl ether system completely suppressed the formation of this by-product without reducing the enantioselectivity. Although the heterogeneous systems were characterised by a drop in catalytic activity the system could be recycled up to five times without any loss in conversion or ee.

Mandelohydroxamic acid as ligand for copper(II) 15-metallacrown-5 lanthanide(III) and copper(II) 15-metallacrown-5 uranyl complexes

The formation of pentanuclear copper(ii) complexes with the mandelohydroxamic ligand was studied in solution by electrospray ionization mass spectrometry (ESI-MS), absorption spectrophotometry, circular dichroism and H-1 NMR spectroscopy. The presence of lanthanide(iii) or uranyl ions is essential for the self-assembly of the 15-metallacrown-5 compounds. The negative mode ESI-MS spectra of solutions containing copper(II), mandelohydroxamic acid and lanthanide(iii) ions (Ln = La, Ce, Nd, Eu, Gd, Dy, Er, Tm, Lu, Y) or uranyl in the ratio 5:5:1 showed only the peaks that could be unambiguously assigned to the following intact molecular ions: {Ln(NO3)(2)[15-MCuIIN(MHA)-5](2-)}(-) and {Ln(NO3)[15-MCCuIIN(MHA)-5](3-)}(-), where MHA represents doubly deprotonated mandelohydroxamic acid. The NMR spectra of the pentanuclear species revealed only one set of peaks indicating a fivefold symmetry of the complex. The pentanuclear complexes synthesized with the enantiomerically pure R- or S-forms of mandelohydroxamic acid ligand, showed circular dichroism spectra which were mirror images of each other. The pentanuclear complex made from the racemic form of the ligand showed no signals in the CD spectrum. The UV/ Vis titration experiments revealed that the order in which the metal salts are added to the solution of the mandelohydroxamic acid ligand is crucial for the formation of metallacrown complexes. The addition of copper(ii) to the solutions containing mandelohydroxamic acid and neodymium(iii) in a 5:1 ratio lead to the formation of a pentanuclear complex in solution. In contrary, titration of lanthanide(iii) salt to the solution containing copper(ii) and mandelohydroxamic acid did not show any evidence for the formation of pentanuclear species. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Coordination Properties of Ionic Liquid-Mediated Chromium(II) and Copper(II) Chlorides and Their Complexes with Glucose

The structural and coordination properties of complexes formed upon the interaction of copper(II) and chromium(II) chlorides with diallrylimidazolium chloride (RMlm(+)Cl(-)) ionic liquids and glucose are studied by a combination of density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS). In the absence of the carbohydrate substrate, isolated mononuclear four-coordinated MeCl42- species (Me = Cu, Cr) dominate in the ionic liquid solution. The organic part of the ionic liquid does not directly interact with the metal centers. The interactions between the RMlm(+) cations and the anionic metal chloride complexes are limited to hydrogen bonding with the basic Cl- ligands and the overall electrostatic stabilization of the anionic metal complexes. Exchange of Cl ligands by a hydroxyl group of glucose is only favorable for CrCl42-. For Cu2+ complexes, the formation of hydrogen bonded complexes between CuCl42- and glucose is preferred. No preference for the coordination of metal chloride species to specific hydroxyl group of the carbohydrate is found. The formation of binuclear metal chloride complexes is also considered. The reactivity and selectivity patterns of the Lewis acid catalyzed reactions of glucose are discussed in the framework of the obtained results.

Accumulation, Subcellular Distribution and Toxicity of Copper in Earthworm (Eisenia fetida) in the Presence of Ciprofloxacin

Land application of wastes from concentrated animal feeding operations results in accumulation of copper (Cu) and antimicrobials in terrestrial systems. Interaction between Cu and antimicrobials may change Cu speciation in soil solution, and affect Cu bioavailability and toxicity. In this study, earthworms were exposed to quartz sand percolated with different concentrations of Cu and ciprofloxacin (CIP). Copper uptake by earthworms, its subcellular partition, and toxicity were studied. An increase in the applied CIP decreased the free Cu ion concentration in external solution and mortalities of earthworm, while Cu contents in earthworms increased. Copper and CIP in earthworms were fractionated into five fractions: a granular fraction (D), a fraction consisting of tissue fragments, cell membranes, and intact cells (E), a microsomal fraction (F), a denatured proteins fraction (G), and a heat-stable proteins fraction (H). Most of the CIP in earthworms was in fraction H. Copper was redistributed from the metal-sensitive fraction E to fractions D, F, G, and H with increasing CIP concentration. These results challenge the free ion activity model and suggested that Cu may be partly taken up as Cu-CIP complexes in earthworms, changing the bioavailability, subcellular distribution, and toxicity of Cu to earthworms.

Multiscale simulation of nanometric cutting of single crystal copper and its experimental validation

In this paper a multiscale simulation study was carried out in order to gain in-depth understanding of machining mechanism of nanometric cutting of single crystal copper. This study was focused on the effects of crystal orientation and cutting direction on the attainable machined surface quality. The machining mechanics was analyzed through cutting forces, chip formation morphology, generation and evolution of defects and residual stresses on the machined surface. The simulation results showed that the crystal orientation of the copper material and the cutting direction significantly influenced the deformation mechanism of the workpiece materials during the machining process. Relatively lower cutting forces were experienced while selecting crystal orientation family {1 1 1}. Dislocation movements were found to concentrate in front of the cutting chip while cutting on the (1 1 1) surface along the View the MathML source cutting direction thus, resulting in much smaller damaged layer on the machined surface, compared to other orientations. This crystal orientation and cutting direction therefore recommended for nanometric cutting of single crystal copper in practical applications. A nano-scratching experiment was performed to validate the above findings.

Preliminary investigation of mixed adsorbents for the removal of copper and methylene blue from aqueous solutions

With most recent studies being focused on the development of
advanced chemical adsorbents, this paper investigates the possibility of
using two natural low-cost materials for selective adsorption. Multiadsorbent
systems containing tea waste and dolomite have been tested for
their effectiveness in the removal of copper and methylene blue from
aqueous solutions. The effects of contact time, solution pH and
adsorption isotherms on the sorption behaviour were investigated. The
Langmuir and Freundlich isotherms adequately described the adsorption of
copper ions and methylene blue by both materials in different systems.
The highest adsorption capacities for Cu and MB were calculated as 237.7
at pH 4.5 and 150.44 mg.g‒1 at pH 7 for DO and TW+DO respectively. Tea
waste (TW) and dolomite (DO) were characterized by Fourier transform
infrared spectroscopy, scanning electron microscopy and Energy dispersive
X-ray analysis. The removal of Cu and MB by dolomite was mainly via
surface complexation while physisorption was responsible for most of the
Cu and MB adsorption onto tea waste. Identifying the fundamental mechanisms and behaviour is key to the development of practical multi-adsorbent packed columns.

Properties of Super-Hydrophobic Copper and Stainless Steel Meshes: Applications in Controllable Water Permeation and Organic Solvents/Water Separation

The wettability and hydrophobicity of super-hydrophobic (SH) meshes is greatly influenced by their topographic structures, chemical composition and coating process. In this study, the properties of copper and stainless steel meshes, coated with super-hydrophobic electrolessly deposited silver were investigated. A new method to test the pressure resistance of super-hydrophobic mesh was applied to avoid any deformation of mesh. Results showed that SH copper mesh and SH stainless steel meshes with the same pore size have almost the same contact angle and the same hydrophobicity. SH copper mesh with a pore size of 122 μm can resist water pressure of 4900 Pa and a decrease of pore size of mesh can increase the pressure resistance of SH copper mesh. The SH copper mesh modified with 0.1 M HS(CH2)10COOH solution in ethanol has a controllable water permeation property by simply adjusting the pH of water solution. SH copper mesh shows super-oleophilicity with organic solvents and so with a water contact angle of 0° and it can be an effective tool for organic solvents/water separation. The separation efficiency of SH copper mesh for separating mixtures of organic solvent and water can be as high as 99.8%.

Facile synthesis of copper-manganese spinel anodes with high capacity and cycling performance for lithium-ion batteries

Copper-manganese spinel containing anodes were synthesized by a facile sol-gel method and evaluated in lithium-ion battery applications for the first time. The synergistic effects between copper-manganese and the aqueous binder (sodium carboxymethyl cellulose) provided a high specific capacity and excellent cycling performance. It was found that the specific capacity of the copper-manganese spinel remained at 608 mAh g⁻¹ after 100 cycles at a current density of 200 mA g⁻¹. Furthermore, a relatively high reversible capacity of 278 mAh g⁻¹ could be obtained at a current density of 2000 mA g⁻¹, indicating a good rate capability. These studies suggest that copper-manganese spinel is a promising material for lithium-ion battery applications due to a combination of good electrochemical performance and low cost.

An array-based study of reactivity under solvent-free mechanochemical conditions-insights and trends

An array-based approach is put forward to obtain insight into reactivity under mechanochemical solvent-free conditions. We describe a survey of sixty potential reactions between twelve metal salts MX2 {(M = Cu, X-2 = (OAc)(2), (HCO2)(2), (F3CCO2)(2), (acac)(2), (F(6)acac)(2), (NO3)(2), SO4; M = Ni, X-2 = (OAc)(2), (NO3)(2), SO4; M = Zn, X-2 (OAc)(2), (NO3)(2)} and five bridging organic ligands {isonicotinic acid (HINA), 1,4-benzenedicarboxylic acid (H2BDC), acetylenedicarboxylic acid (H(2)ADC), 1,3,5-benzenetricarboxylic acid (H3BTC), 4,4'-bipyridyl (BIPY). Reaction conditions involved a ball mill, applied for 15 min at 30 Hz, without external heating. When examined by XRPD, forty of the combinations gave detectable reactions, thirty-eight with crystalline products. Of these, twenty-nine reactions were quantitative (consuming all of at least one reactant). Comparison of XRPD patterns with patterns simulated from single crystal X-ray diffraction data in the Cambridge Structural Database allowed structural identification of six products. Of particular interest are the microporous framework materials [Cu(INA)(2)] and [Cu-3(BTC)(2)] (HKUST-1) obtained by reaction of the corresponding carboxylic acids with copper acetate. Other non-porous polymers with 3-dimensional connectivity, [Ni(ADC)(H2O)(4)], or 1-dimensional connectivity, [Cu(acac)(2)(BIPY)] and [Cu(F6acac)(BIPY)] were also obtained. Reaction between zinc acetate and H2ADC gave a new product which had not previously been characterised by single-crystal X-ray crystallography, but whose XRPD pattern suggests that it is isostructural with the known nickel polymer [Ni(ADC)(H2O)(4)]. Two further isostructural nickel and zinc products were obtained in reactions between HINA and nickel nitrate and zinc nitrate. Trends observed within the array are discussed. Copper acetate and copper formate were the most effective starting materials for reaction with carboxylic acids, potentially related to the basicity of their anions and the solvating effects of the formic and acetic acid byproducts. Amongst the ligands there was a general negative corelation between melting point and reactivity. The issue of pore templating in microporous phases and the generation of new structures is also discussed in relation to the Cu(INA)(2), Cu-3(BTC)(2) and nickel nitrate-BIPY systems. Overall, the study suggests that mechanochemical reactivity between metal salts and organic ligands under solvent free conditions is remarkably general. Use of array-based approaches as demonstrated here is advocated a useful way to reveal underlying trends in reactivity under solvent free mechanochemical conditions and to highlight particular cases for more detailed study.