[Influence of heavy metals on surfactants synthesis by Nocardia vaccinii IMV B-7405].

PubMed

Pirog, T P; Konon, A D; Pokora, K A; Shevchuk, T A; Iutinskaia, G A

2014-01-01

The production of surfactants by Nocardia vaccinii IMV B-7405 in glycerol -and hydrocarbon-containing medium after addition Cd(3+) Pb(2+) and Cu(2+) was investigated. It was established that the introduction of 0.1 mM Cu(2+) in the exponential growth phase of IMV B-7405 strain or simultaneous addition of Cu(2+) (0.1 mM) and Cd(2+) (0.3 mM), Cu(2+) (0.1 mM) and Pb(2+) (0.3 mM) in stationary phase was accompanied by the increase of conditional concentration of the surfactant (by 53 and 20-26%, respectively) compared with indexes in the medium without metals cations. It was established that the surfactants of N. vaccinii IMV B-7405 possessed protective functions from heavy metals influence. After surfactants elimination the survival of cells of strain IMV B-7405 in the presence of Cu(2+) (1.5-2.5 mM), Cd(2+) or Pb(2+) (0.1-0.3 mM) decreased a few times (to 5-45%). The inhibition action of Cu(2+) on alkane hydroxylase activity (the first enzyme of hydrocarbon catabolism) and stimulation--on phosphoenolpyruvate synthetase (enzyme of surface-active glycolipids biosynthesis) in MB B-7405 have been established.

Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO2

PubMed Central

Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

2016-01-01

In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO2 powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO2 films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO2 up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO2. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model. PMID:28773351

Kinetics of Isothermal Reactive Diffusion Between Solid Cu and Liquid Sn

NASA Astrophysics Data System (ADS)

O, M.; Suzuki, T.; Kajihara, M.

2018-01-01

The Cu/Sn system is one of the most fundamental and important metallic systems for solder joints in electric devices. To realize reliable solder joints, information on reactive diffusion at the solder joint is very important. In the present study, we experimentally investigated the kinetics of the reactive diffusion between solid Cu and liquid Sn using semi-infinite Cu/Sn diffusion couples prepared by an isothermal bonding technique. Isothermal annealing of the diffusion couple was conducted in the temperature range of 533-603 K for various times up to 172.8 ks (48 h). Using annealing, an intermetallic layer composed of Cu6Sn5 with scallop morphology and Cu3Sn with rather uniform thickness is formed at the original Cu/Sn interface in the diffusion couple. The growth of the Cu6Sn5 scallop occurs much more quickly than that of the Cu3Sn layer and thus predominates in the overall growth of the intermetallic layer. This tendency becomes more remarkable at lower annealing temperatures. The total thickness of the intermetallic layer is proportional to a power function of the annealing time, and the exponent of the power function is close to unity at all the annealing temperatures. This means that volume diffusion controls the intermetallic growth and the morphology of the Cu6Sn5/Sn interface influences the rate-controlling process. Adopting a mean value of 0.99 for the exponent, we obtain a value of 26 kJ/mol for the activation enthalpy of the intermetallic growth.

Far-infrared study of the mechanochemically synthesized Cu2FeSnS4 (stannite) nanocrystals

NASA Astrophysics Data System (ADS)

Trajic, J.; Romcevic, M.; Paunovic, N.; Curcic, M.; Balaz, P.; Romcevic, N.

2018-05-01

The analysis of the optical properties of mechanochemically synthesized stannite Cu2FeSnS4 nanocrystals has been performed using far-infrared spectroscopy. The Cu2FeSnS4 stannite nanocrystals were synthesized mechanochemically from elemental precursors Cu, Fe, Sn, and S. Milling time was 45, 60, 90 and 120 min. Reflectivity spectra were analyzed using the classical form of the dielectric function, which includes the phonon and the free carrier contribution. The influence of milling time on synthesis of stannite Cu2FeSnS4 is observed. Among the modes that are characteristic for the stannite Cu2FeSnS4, we registered the modes of binary phases of FeS and SnS. The total disappearance of the binary phases of FeS and SnS and forming pure Cu2FeSnS4 is observed when the milling time is 120 min. Effective permittivity of Cu2FeSnS4 and binary phases of FeS and SnS were modeled by Maxwell - Garnet approximation.

Influence of Na and Ga on the electrical properties of perfect 60° dislocations in Cu(In, Ga)Se2 thin-film photovoltaic absorbers

NASA Astrophysics Data System (ADS)

Barragan-Yani, D.; Albe, K.

2018-04-01

The segregation of GaIn and NaCu to perfect 60° dislocations in CuIn1-xGaxSe2 is investigated by means of density functional theory calculations. We find that the segregation process is mainly driven by the elastic interaction of both defect types with the strain field of the dislocation. GaIn moves into the negatively strained region, while NaCu is found in the positively strained region. We show that both defects affect the electronic defect levels induced by the dislocation core and GaIn is able to passivate the β-core in CuInSe2. This result indicates that β-cores are inactive in CuIn1-xGaxSe2. NaCu; however, they do not have a significant effect on the electrical properties of the studied dislocation cores. Therefore, the experimentally observed sodium segregation to dislocation cores in CuIn1-xGaxSe2 cannot be considered as the passivation mechanism of the electrically active cores in that material.

First-principles surface interaction studies of aluminum-copper and aluminum-copper-magnesium secondary phases in aluminum alloys

NASA Astrophysics Data System (ADS)

da Silva, Thiago H.; Nelson, Eric B.; Williamson, Izaak; Efaw, Corey M.; Sapper, Erik; Hurley, Michael F.; Li, Lan

2018-05-01

First-principles density functional theory-based calculations were performed to study θ-phase Al2Cu, S-phase Al2CuMg surface stability, as well as their interactions with water molecules and chloride (Cl-) ions. These secondary phases are commonly found in aluminum-based alloys and are initiation points for localized corrosion. Density functional theory (DFT)-based simulations provide insight into the origins of localized (pitting) corrosion processes of aluminum-based alloys. For both phases studied, Cl- ions cause atomic distortions on the surface layers. The nature of the distortions could be a factor to weaken the interlayer bonds in the Al2Cu and Al2CuMg secondary phases, facilitating the corrosion process. Electronic structure calculations revealed not only electron charge transfer from Cl- ions to alloy surface but also electron sharing, suggesting ionic and covalent bonding features, respectively. The S-phase Al2CuMg structure has a more active surface than the θ-phase Al2Cu. We also found a higher tendency of formation of new species, such as Al3+, Al(OH)2+, HCl, AlCl2+, Al(OH)Cl+, and Cl2 on the S-phase Al2CuMg surface. Surface chemical reactions and resultant species present contribute to establishment of local surface chemistry that influences the corrosion behavior of aluminum alloys.

Analysis of localized surface plasmon resonances in gold nanoparticles surrounded by copper oxides

NASA Astrophysics Data System (ADS)

Stamatelatos, A.; Sousanis, A.; Chronis, A. G.; Sigalas, M. M.; Grammatikopoulos, S.; Poulopoulos, P.

2018-02-01

Au-doped Cu thin films are produced by co-deposition of Au and Cu via radiofrequency magnetron sputtering in a vacuum chamber with a base pressure of 1 × 10-7 mbar. After post annealing in a furnace with air, one may obtain either Au-Cu2O or Au-CuO nanocomposite thin films. The presence of Au does not have any considerable influence on the position of the optical band gap of the oxides. Only the Au-CuO system shows well-formed localized surface plasmonic resonances with Gaussian shape. We study systematically the plasmonic behavior of the nanocomposites as a function of the gold concentration, annealing time, and film thickness. The intensity of the resonances, their position, and width are intensely affected by all these parameters. The experimental results are compared with respect to rigorous theoretical calculations. The similarities and differences between experiment and theory are discussed.

Chronopharmacological effects of growth hormone on the executive function and oxidative stress response in rats.

PubMed

Ferrari, Carlos K B; França, Eduardo L; Monteiro, Luciane A; Santos, Bruno L; Pereira-Junior, Alfredo; Honorio-França, Adenilda C

2017-01-01

To investigate the chronopharmacological effects of growth hormone on executive function and the oxidative stress response in rats. Fifty male Wistar rats (36-40 weeks old) had ad libitum access to water and food and were separated into four groups: diurnal control, nocturnal control, diurnal GH-treated, and nocturnal GH-treated animals. Levels of Cu, Zn superoxide dismutase (Cu, Zn-SOD), and superoxide release by spleen macrophages were evaluated. For memory testing, adaptation and walking in an open field platform was used. GH-treated animals demonstrated better performance in exploratory and spatial open-field tests. The latency time in both GH-treated groups was significantly lower compared with the latency time of the control groups. The diurnal GH treatment did not stimulate superoxide release but increased the CuZn-SOD enzyme levels. The nocturnal GH treatment did not influence the superoxide release and CuZn-SOD concentration. GH treatment also resulted in heart atrophy and lung hypertrophy. Growth hormone treatment improved the performance of executive functions at the cost of oxidative stress triggering, and this effect was dependent on the circadian period of hormone administration. However, GH treatment caused damaging effects such as lung hypertrophy and heart atrophy.

Design parameters for tuning the type 1 Cu multicopper oxidase redox potential: insight from a combination of first principles and empirical molecular dynamics simulations.

PubMed

Hong, Gongyi; Ivnitski, Dmitri M; Johnson, Glenn R; Atanassov, Plamen; Pachter, Ruth

2011-04-06

The redox potentials and reorganization energies of the type 1 (T1) Cu site in four multicopper oxidases were calculated by combining first principles density functional theory (QM) and QM/MM molecular dynamics (MD) simulations. The model enzymes selected included the laccase from Trametes versicolor, the laccase-like enzyme isolated from Bacillus subtilis, CueO required for copper homeostasis in Escherichia coli, and the small laccase (SLAC) from Streptomyces coelicolor. The results demonstrated good agreement with experimental data and provided insight into the parameters that influence the T1 redox potential. Effects of the immediate T1 Cu site environment, including the His(N(δ))-Cys(S)-His(N(δ)) and the axial coordinating amino acid, as well as the proximate H(N)(backbone)-S(Cys) hydrogen bond, were discerned. Furthermore, effects of the protein backbone and side-chains, as well as of the aqueous solvent, were studied by QM/MM molecular dynamics (MD) simulations, providing an understanding of influences beyond the T1 Cu coordination sphere. Suggestions were made regarding an increase of the T1 redox potential in SLAC, i.e., of Met198 and Thr232 in addition to the axial amino acid Met298. Finally, the results of this work presented a framework for understanding parameters that influence the Type 1 Cu MCO redox potential, useful for an ever-growing range of laccase-based applications. © 2011 American Chemical Society

Structural and magnetic characterization of copper sulfonated phthalocyanine grafted onto treated polyethylene

NASA Astrophysics Data System (ADS)

Reznickova, A.; Kolska, Z.; Orendac, M.; Cizmar, E.; Sajdl, P.; Svorcik, V.

2016-08-01

This study focuses on high density polyethylene (HDPE) activated by Ar plasma treatment, subsequently grafted with copper sulfonated phthalocyanine (CuPc) especially pointing out to the surface and magnetic properties of those composites. Properties of pristine PE and their plasma treated counterparts were studied by different experimental techniques: X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, zeta potential and by electron spin resonance (ESR). XPS analysis confirmed the successful grafting of phthalocyanine. The highest absorption was found for the sample grafted with bCuPc for 1 h. Electrokinetic analysis also confirmed the plasma treatment and also subsequent CuPc grafting influence significantly the surface chemistry and charge. These results correspond well with XPS determination. ESR studies confirmed the presence of CuPc grafted on HDPE. It was found, that grafting is mediated by magnetically inactive functional groups, rather than radicals. Magnetic properties of CuPc do not seem to change significantly after grafting CuPc on polyethylene surface.

The link between callous-unemotional traits and neural mechanisms of reward processing: An fMRI study.

PubMed

Veroude, Kim; von Rhein, Daniel; Chauvin, Roselyne J M; van Dongen, Eelco V; Mennes, Maarten J J; Franke, Barbara; Heslenfeld, Dirk J; Oosterlaan, Jaap; Hartman, Catharina A; Hoekstra, Pieter J; Glennon, Jeffrey C; Buitelaar, Jan K

2016-09-30

Callous-unemotional (CU) traits, i.e., unconcernedness and lack of prosocial feelings, may manifest in Conduct Disorder (CD), but also in Oppositional Defiant Disorder (ODD) and Attention Deficit Hyperactivity Disorder (ADHD). These disorders have been associated with aberrant reward processing, while the influence of CU traits is unclear. Using functional Magnetic Resonance Imaging (fMRI), we examined whether CU traits affect the neural circuit for reward. A Monetary Incentive Delay (MID) task was administered to 328 adolescents and young adults with varying levels of CU traits: 40 participants with ODD/CD plus ADHD, 101 participants with ADHD only, 84 siblings of probands with ADHD and 103 typically developing (TD) individuals. During reward anticipation, CU traits related negatively to medial prefrontal cortex (mPFC) activity, independent of ADHD symptoms and ODD/CD diagnosis. Our results indicate that CU traits are a valuable dimension for assessing the neural basis of reward processing. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Dual structural transition in small nanoparticles of Cu-Au alloy

NASA Astrophysics Data System (ADS)

Gafner, Yuri; Gafner, Svetlana; Redel, Larisa; Zamulin, Ivan

2018-02-01

Cu-Au alloy nanoparticles are known to be widely used in the catalysis of various chemical reactions as it was experimentally defined that in many cases the partial substitution of copper with gold increases catalytic activity. However, providing the reaction capacity of alloy nanoparticles the surface electronic structure strongly depends on their atomic ordering. Therefore, to theoretically determine catalytic properties, one needs to use a most real structural model complying with Cu-Au nanoparticles under various external influences. So, thermal stability limits were studied for the initial L12 phase in Cu3Au nanoalloy clusters up to 8.0 nm and Cu-Au clusters up to 3.0 nm at various degrees of Au atom concentration, with molecular dynamics method using a modified tight-binding TB-SMA potential. Dual structural transition L12 → FCC and further FCC → Ih is shown to be possible under the thermal factor in Cu3Au and Cu-Au clusters with the diameter up to 3.0 nm. The temperature of the structural transition FCC → Ih is established to decrease for small particles of Cu-Au alloy under the increase of Au atom concentration. For clusters with this structural transition, the melting point is found to be a linear increasing function of concentration, and for clusters without FCC → Ih structural transition, the melting point is a linear decreasing function of Au content. Thus, the article shows that doping Cu nanoclusters with Au atoms allows to control the forming structure as well as the melting point.

Assesment of influncing factors on mechanical and electrical properties of Al/Cu joints

NASA Astrophysics Data System (ADS)

Selvaraj, R. Meby; Hynes, N. Rajesh Jesudoss

2018-05-01

Joining of dissimilar materials opens up challenging opportunities in todays technology. Al/Cu weldments are used in applications that demands corrosion resistance, thermal and electrical conducting properties. In dissimilar joining mechanical and thermal properties result in large stress gradients during heating. The Al-Cu joints are lighter, cheaper and have conductivity equal to copper alloy. The main scope of this study is to assess the influencing factors of Al/Cu joints in mechanical and electrical properties. It includes the influence of the dilution between the base metals, influence of physical properties, influence of welding parameters, influence of filler metal, influence of heat treatment, and influence of electrical properties

Features of Electron Density Distribution in Delafossite Cualo2

NASA Astrophysics Data System (ADS)

Pogoreltsev, A. I.; Schmidt, S. V.; Gavrilenko, A. N.; Shulgin, D. A.; Korzun, B. V.; Matukhin, V. L.

2015-07-01

We have used pulsed 63,65Cu nuclear quadrupole resonance at room temperature to study the semiconductor compound CuAlO2 with a delafossite crystal structure, and we have determined the quadrupole frequency νQ = 28.12 MHz and the asymmetry parameter η ~ 0, which we used to study the features of the electron density distribution in the vicinity of the quadrupolar nucleus. In order to take into account the influence of correlation effects on the electric field gradient, we carried out ab initio calculations within the density functional theory (DFT) approximation using a set of correlation functionals VWN1RPA, VWN5, PW91LDA, CPW91, and B3LYP1. We mapped the electron density distribution in the vicinity of the quadrupolar copper nucleus for the Cu7Al6o{14/- 1} cluster and we calculated the size of the LUMO-HOMO gap, Δ ~ 3.33 eV. We established the anisotropy of the spatial electron density distribution. Based on analysis of the electron density distribution obtained, we suggest that the bond in CuAlO2 is not purely covalent.

Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites.

PubMed

Miglio, Anna; Heinrich, Christophe P; Tremel, Wolfgang; Hautier, Geoffroy; Zeier, Wolfgang G

2017-09-01

Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu 2 ZnGeS 4- x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlying bonding interactions at the band edges can help design properties of these quaternary chalcopyrites for photovoltaic and thermoelectric applications.

Influence of atomic tip structure on the intensity of inelastic tunneling spectroscopy data analyzed by combined scanning tunneling spectroscopy, force microscopy, and density functional theory

NASA Astrophysics Data System (ADS)

Okabayashi, Norio; Gustafsson, Alexander; Peronio, Angelo; Paulsson, Magnus; Arai, Toyoko; Giessibl, Franz J.

2016-04-01

Achieving a high intensity in inelastic scanning tunneling spectroscopy (IETS) is important for precise measurements. The intensity of the IETS signal can vary by up to a factor of 3 for various tips without an apparent reason accessible by scanning tunneling microscopy (STM) alone. Here, we show that combining STM and IETS with atomic force microscopy enables carbon monoxide front-atom identification, revealing that high IETS intensities for CO/Cu(111) are obtained for single-atom tips, while the intensity drops sharply for multiatom tips. Adsorption of the CO molecule on a Cu adatom [CO/Cu/Cu(111)] such that the molecule is elevated over the substrate strongly diminishes the tip dependence of IETS intensity, showing that an elevated position channels most of the tunneling current through the CO molecule even for multiatom tips, while a large fraction of the tunneling current bypasses the CO molecule in the case of CO/Cu(111).

High-purity Cu nanocrystal synthesis by a dynamic decomposition method.

PubMed

Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

2014-12-01

Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.

High-purity Cu nanocrystal synthesis by a dynamic decomposition method

NASA Astrophysics Data System (ADS)

Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

2014-12-01

Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.

Photocatalytic property and structural stability of CuAl-based layered double hydroxides

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

Lv, Ming; Liu, Haiqiang, E-mail: Liuhaiqiang1980@126.com

2015-07-15

Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) were successfully synthesized by coprecipitation. Powder X-ray diffraction (XRD), inductively coupled plasma atomic emission spectrometry (ICP-AES) and UV–Vis diffuse reflectance spectrum (UV–vis) were used to confirm the formation of as-synthesized solids with good crystal structure. The photocatalytic activity of those LDH materials for CO{sub 2} reduction under visible light was investigated. The experimental results show that CuNiAl-LDHs with narrowest band gap and largest surface areas behave highest efficiency for methanol generation under visible light compared with CuMgAl-LDHs and CuZnAl-LDHs. The CuNiAL-LDH showed high yield for methanol production i.e. 0.210more » mmol/g h, which was high efficient. In addition, the influence of the different M{sup 2+} on the structures and stability of the CuMAl-LDHs was also investigated by analyzing the geometric parameters, electronic arrangement, charge populations, hydrogen-bonding, and binding energies by density functional theory (DFT) analysis. The theoretical calculation results show that the chemical stability of LDH materials followed the order of CuMgAl-LDHs>CuZnAl-LDHs>CuNiAl-LDHs, which is just opposite with the photocatalytic activity and band gaps of three materials. - Graphical abstract: The host–guest calculation models and XRD patterns of CuMAl-LDHs: CuMgAl-LDHs (a), CuZnAl-LDHs (b) and CuNiAl-LDHs (c). - Highlights: • Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) has been synthesized. • CuMgNi shows narrower band gap and more excellent textural properties than other LDHs. • The band gap: CuMgAl« less

Callous-unemotional behaviors in early childhood: Genetic and environmental contributions to stability and change.

PubMed

Flom, Megan; Saudino, Kimberly J

2017-10-01

Callous-unemotional (CU) behaviors demonstrate meaningful individual differences in early childhood, even in nonclinical samples with low mean levels of CU, but the factors underlying this variation have not been examined. This study investigated genetic and environmental contributions to individual differences and to sources of continuity and change in CU in toddler twins (145 monozygotic, 169 dizygotic) assessed at ages 2 and 3 years. CU, as assessed by the Child Behavior Checklist 1.5-5 (Achenbach & Rescorla, 2000), was moderately stable across age (r = .45, p < .0001). Longitudinal biometric analyses revealed genetic and nonshared environmental influences on CU at both ages, with no significant contribution from shared environmental factors. Stability from age 2 to 3 was due to genetic factors, whereas change was due to both genetic and nonshared environmental influences. This genetic and nonshared environmental change was substantial, suggesting malleability of CU in early childhood. Over 50% of the genetic influences and 100% of the nonshared environmental influences on CU at age 3 were independent of those that operated at age 2. Implications of novel sources of variance across age are discussed.

Preparation and cupric ion release behavior of Cu/LDPE porous composites with tunable pore morphology for intrauterine devices.

PubMed

Xiao, Lian; Xia, Xianping; Xie, Changsheng; Ge, Man; Xiao, Cheng; Cai, Shuizhou

2013-07-01

Copper/low-density polyethylene (Cu/LDPE) porous composites are novel materials for copper-containing intrauterine devices (Cu-IUDs). Here we report a method, i.e., by changing the mass ratio of two kinds of porogens that have different melting points through the combined techniques of injection molding and particulate leaching, to prepare the Cu/LDPE porous composites with tunable pore morphology. After these Cu/LDPE porous composites with different pore morphologies were obtained, the influences of pore morphologies on their cupric ion release behaviors were studied. The results show that the pore morphology has great influence on the cupric ion release behavior of Cu/LDPE porous composites. This phenomenon is caused by the different influences of different pore morphologies on the effective porosity and the surface hydrophilicity. And those results can be applied to guide the fabrication of Cu/LDPE porous composite Cu-IUDs with minimal weight at an appropriate cupric ion release rate. Copyright © 2013 Elsevier B.V. All rights reserved.

Influences on Distribution of Solute Atoms in Cu-8Fe Alloy Solidification Process Under Rotating Magnetic Field

NASA Astrophysics Data System (ADS)

Zou, Jin; Zhai, Qi-Jie; Liu, Fang-Yu; Liu, Ke-Ming; Lu, De-Ping

2018-05-01

A rotating magnetic field (RMF) was applied in the solidification process of Cu-8Fe alloy. Focus on the mechanism of RMF on the solid solution Fe(Cu) atoms in Cu-8Fe alloy, the influences of RMF on solidification structure, solute distribution, and material properties were discussed. Results show that the solidification behavior of Cu-Fe alloy have influenced through the change of temperature and solute fields in the presence of an applied RMF. The Fe dendrites were refined and transformed to rosettes or spherical grains under forced convection. The solute distribution in Cu-rich phase and Fe-rich phase were changed because of the variation of the supercooling degree and the solidification rate. Further, the variation in solute distribution was impacted the strengthening mechanism and conductive mechanism of the material.

Facile room-temperature synthesis of carboxylated graphene oxide-copper sulfide nanocomposite with high photodegradation and disinfection activities under solar light irradiation

PubMed Central

Yu, Shuyan; Liu, Jincheng; Zhu, Wenyu; Hu, Zhong-Ting; Lim, Teik-Thye; Yan, Xiaoli

2015-01-01

Carboxylic acid functionalized graphene oxide-copper (II) sulfide nanoparticle composite (GO-COOH-CuS) was prepared from carboxylated graphene oxide and copper precursor in dimethyl sulfoxide (DMSO) by a facile synthesis process at room temperature. The high-effective combination, the interaction between GO-COOH sheets and CuS nanoparticles, and the enhanced visible light absorption were confirmed by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (DRS) and Photoluminescence (PL) spectra. The as-synthesized GO-COOH-CuS nanocomposite exhibited excellent photocatalytic degradation performance of phenol and rhodamine B, high antibacterial activity toward E. coli and B. subtilis, and good recovery and reusability. The influence of CuS content, the synergistic reaction between CuS and GO-COOH, and the charge-transfer mechanism were systematically investigated. The facile and low-energy synthesis process combined with the excellent degradation and antibacterial performance signify that the GO-COOH-CuS has a great potential for water treatment application. PMID:26553709

Synthesis methods influence characteristics, behaviour and toxicity of bare CuO NPs compared to bulk CuO and ionic Cu after in vitro exposure of Ruditapes philippinarum hemocytes.

PubMed

Volland, Moritz; Hampel, Miriam; Katsumiti, Alberto; Yeste, María Pilar; Gatica, José Manuel; Cajaraville, Miren; Blasco, Julián

2018-06-01

Copper oxide (CuO) nanoparticles (NPs) are increasingly investigated, developed and produced for a wide range of industrial and consumer products. Notwithstanding their promising novel applications, concern has been raised that their increased use and disposal could consequently increase their release into marine systems and potentially affect species within. To date the understanding of factors and mechanisms of CuO (nano-) toxicity to marine invertebrates is still limited. Hence, we studied the characteristics and behaviour of two commercially available CuO NPs of similar size, but produced employing distinct synthesis methods, under various environmentally and experimentally relevant conditions. In addition, cell viability and DNA damage, as well as gene expression of detoxification, oxidative stress, inflammatory response, DNA damage repair and cell death mediator markers were studied in primary cultures of hemocytes from the marine clam Ruditapes philippinarum and, where applicable, compared to bulk CuO and ionic Cu (as CuSO 4 ) behaviour and effects. We found that the synthesis method can influence particle characteristics and behaviour, as well as the toxicity of CuO NPs to Ruditapes philippinarum hemocytes. Our results further indicate that under the tested conditions aggregating behaviour influences the toxicity of CuO NPs by influencing their rate of extra- and intracellular dissolution. In addition, gene expression analysis identified similar transcriptional de-regulation for all tested copper treatments for the here measured suite of genes. Finally, our work highlights various differences in the aggregation and dissolution kinetics of CuO particles under environmental (marine) and cell culture exposure conditions that need consideration when extrapolating in vitro findings. Copyright © 2018 Elsevier B.V. All rights reserved.

Biokinetics of different-shaped copper oxide nanoparticles in the freshwater gastropod, Potamopyrgus antipodarum

USGS Publications Warehouse

Ramskov, Tina; Croteau, Marie-Noele; Forbes, Valery E.; Selck, Henriette

2015-01-01

Sediment is recognized as a major environmental sink for contaminants, including engineered nanoparticles (NPs). Consequently, sediment-living organisms are likely to be exposed to NPs. There is evidence that both accumulation and toxicity of metal NPs to sediment-dwellers increase with decreasing particle size, although NP size does not always predict effects. In contrast, not much is known about the influence of particle shape on bioaccumulation and toxicity. Here, we examined the influence of copper oxide (CuO) NP shape (rods, spheres, and platelets) on their bioaccumulation kinetics and toxicity to the sediment-dwelling gastropod, Potamopyrgus antipodarum. The influence of Cu added as CuCl2 (i.e., aqueous Cu treatment) was also examined. Exposure to sediment mixed with aqueous Cu or with different-shaped CuO NPs at an average measured exposure concentration of 207 μg Cu per g dry weight sediment for 14 days did not significantly affect snail mortality. However, growth decreased for snails exposed to sediment amended with CuO NP spheres and platelets. P. antipodarum accumulated Cu from all Cu forms/shapes in significant amounts compared to control snails. In addition, once accumulated, Cu was efficiently retained (i.e., elimination rate constants were generally not significantly different from zero). Consequently, snails are likely to concentrate Cu over time, from both aqueous and NP sources, resulting in a high potential for toxicity.

The role of soil biogeochemistry in wine taste: Soil factors influencing grape elemental composition, photosynthetic biomarkers and Cu/Zn isotopic signature of Vitis vinifera

NASA Astrophysics Data System (ADS)

Blotevogel, Simon; Oliva, Priscia; Darrozes, José; Viers, Jérôme; Audry, Stéphane; Courjault-Radé, Pierre; Orgogozo, Laurent; Le Guedard, Marina; Schreck, Eva

2015-04-01

Understanding the influence of soil composition in wine taste is of great economic and environmental interest in France and around the world. Nevertheless the impact of soil composition on wine taste is still controversially discussed. Since inorganic soil components do not have a proper taste and do not enter the plant anyway, their influence needs to be induced by nutrient absorption and its impact on plant functioning and grape composition. Indeed recent development of geological tracers of origin proof the existence of soil chemical and isotopic signatures in wine. However, type and scale of the impact of soil composition on wine taste are not well understood yet, and little experimental evidence exists due to the complexity of mechanisms involved. Thus, to provide evidence for the impact of soil composition on grape composition and potentially wine taste, we studied soil and plant material from two relevant vineyards (Soave, Italia). On those two directly adjacent vineyards, two different wines are produced with the same plant material and cultivation techniques. The vineyards only differ by their underlying bedrock - limestone versus basaltic rock - and thus present suitable conditions for investigating the impact of soil composition on grapes and wine. Pedological and mineralogical parameters were analyzed for the two vineyards whereas chemical extractions (citrate, CaCl2) were performed to determine nutrient bioavailability in both soils. Elemental compositions were determined by ICP-MS analyses in different compartments (soils, vine leaves and grapes). Isotopic fractionation of Cu and Zn was investigated in various samples as source tracers and in order to better understand fractionation mechanisms involved. Finally, plant health was studied using the Omega-3 biomarker which determines the fatty acid composition in vine leaves, directly involved in photosynthetic processes. Results show that the vineyards are characterized by two different soil types due to the geological difference. These soils differ in elemental compositions and bioavailability of mineral nutrients, preconditions for a potential influence on plants and wine. Elemental ratios of soils are partly transmitted to leaves and grapes of correspondent plants, including nutrients such as Ca. Plant photosynthetic functioning is significantly better on the limestone vineyard due to lower Cu bioavailability: Omega-3 values are negatively linked to Cu bioavailability in corresponding soils. These observations suggest a difference in organic molecule synthesis depending on the vineyard soil, which might include components relevant for taste and fermentation. Cu and Zn isotopic ratios do not differ between both soils. The main fractionation of Cu and Zn isotopes occurs at the soil-plant interface making those isotopes suitable tracers for uptake mechanisms. As a result Zn isotope ratios reveal a strong recycling of Zn in the soil-plant continuum. Our results show a significant influence of soil composition on grape composition, plant biochemistry and potentially wine taste. Determination of organic and sensorial composition of grapes and wine is ongoing and will be discussed in further communications.

On the annealing-induced enhancement of the interface properties of NiO:Cu/wet-SiOx/n-Si tunnelling junction solar cells

NASA Astrophysics Data System (ADS)

Yang, Xueliang; Liu, Wei; Chen, Jingwei; Sun, Yun

2018-04-01

Using metal oxides to form a carrier-selective interface on crystalline silicon (c-Si) has recently generated considerable interest for use with c-Si photovoltaics because of the potential to reduce cost. n-type oxides, such as MoO3, V2O5, and WO3, have been widely studied. In this work, a p-type oxide, Cu-doped NiO (NiO:Cu), is explored as a transparent hole-selective contact to n-Si. An ultrathin SiOx layer, fabricated by a wet-chemical method (wet-SiOx), is introduced at the NiO:Cu/n-Si interface to achieve a tunnelling junction solar cell. Interestingly, it was observed that the interface quality of the NiO:Cu/wet-SiOx/n-Si heterojunction was dramatically enhanced by post-deposition annealing (PDA) at a temperature of 200 °C. Our device exhibits an improved power conversion efficiency of 10.8%, which is the highest efficiency among NiO/Si heterojunction photo-electric devices to date. It is demonstrated that the 200 °C PDA treatment enhances the built-in field by a reduction in the interface density of states (Dit) but does not influence the work function of the NiO:Cu thin layer. This stable work function after the PDA treatment is in conflict with the changed built-in field according to the Schottky model. Thus, the Bardeen model is introduced for this physical insight: the enhancement of the built-in field originates from the unpinning of the Fermi levels of NiO:Cu and n-Si by the interface state reduction.

Axial interactions in the mixed-valent CuA active site and role of the axial methionine in electron transfer

PubMed Central

Tsai, Ming-Li; Hadt, Ryan G.; Marshall, Nicholas M.; Wilson, Tiffany D.; Lu, Yi; Solomon, Edward I.

2013-01-01

Within Cu-containing electron transfer active sites, the role of the axial ligand in type 1 sites is well defined, yet its role in the binuclear mixed-valent CuA sites is less clear. Recently, the mutation of the axial Met to Leu in a CuA site engineered into azurin (CuA Az) was found to have a limited effect on E0 relative to this mutation in blue copper (BC). Detailed low-temperature absorption and magnetic circular dichroism, resonance Raman, and electron paramagnetic resonance studies on CuA Az (WT) and its M123X (X = Q, L, H) axial ligand variants indicated stronger axial ligation in M123L/H. Spectroscopically validated density functional theory calculations show that the smaller ΔE0 is attributed to H2O coordination to the Cu center in the M123L mutant in CuA but not in the equivalent BC variant. The comparable stabilization energy of the oxidized over the reduced state in CuA and BC (CuA ∼ 180 mV; BC ∼ 250 mV) indicates that the S(Met) influences E0 similarly in both. Electron delocalization over two Cu centers in CuA was found to minimize the Jahn–Teller distortion induced by the axial Met ligand and lower the inner-sphere reorganization energy. The Cu–S(Met) bond in oxidized CuA is weak (5.2 kcal/mol) but energetically similar to that of BC, which demonstrates that the protein matrix also serves an entatic role in keeping the Met bound to the active site to tune down E0 while maintaining a low reorganization energy required for rapid electron transfer under physiological conditions. PMID:23964128

Evaluation of different isotherm models, kinetic, thermodynamic, and copper biosorption efficiency of Lobaria pulmonaria (L.) Hoffm.

PubMed

Kiliç, Zeynep; Atakol, Orhan; Aras, Sümer; Cansaran-Duman, Demet; Celikkol, Pelin; Emregul, Emel

2014-01-01

The biosorption characteristics of Cu(II) ions from aqueous solution using Lobaria pulmonaria (L.) Hoffm. biomass were investigated. The biosorption efficiency of Cu(II) onto biomass was significantly influenced by the operating parameters. The maximum biosorption efficiency of L. pulmonaria was 65.3% at 10 mg/L initial metal concentration for 5 g/L lichen biomass dosage. The biosorption of Cu(II) ions onto biomass fits the Langmuir isotherm model and the pseudo-second-order kinetic model well. The thermodynamic parameters indicate the feasibility and exothermic and spontaneous nature of the biosorption. The effective desorption achieved with HCl was 96%. Information on the nature of possible interactions between the functional groups of the L. pulmonaria biomass and Cu(II) ions was obtained via Fourier transform infrared (FTIR) spectroscopy. The results indicated that the carboxyl (-COOH) and hydroxyl (-OH) groups of the biomass were mainly involved in the biosorption of Cu(II) onto L. pulmonaria biomass. The L. pulmonaria is a promising biosorbent for Cu(lI) ions because of its availability, low cost, and high metal biosorption and desorption capacities. Lobaria pulmonaria is a promising biosorbent for Cu(II) ions because of its availability, low cost, and high metal biosorption and desorption capacities. To the best of our knowledge, this is the first paper on the biosorption Cu by L. pulmonaria.

Structural, optical and electronic properties of indium sulfide compositions under influence of copper impurity produced by chemical method

NASA Astrophysics Data System (ADS)

Esmaili, Parisa; Kangarlou, Haleh; Savaloni, Hadi; Ghorannevis, Mahmood

Aqueous solutions with 70 °C and pH = 2.5 constant values were prepared from convenient chemical compounds to produce In2S3: Cu crystals and thin films. Crystal compositions were grown in this solution under special conditions. Micrographs showed amorphous In2S3 orange powder and transparent vitreous pieces of CuInS2 crystals. Indium sulfide films were produced using the same solution in CBD method, on the glass substrates at different [Cu/In] molar ratio concentrations. Cu+ ions by different concentration doped from copper chloride source into In2S3 films. The produced films were post-annealed at 400 °C for about 1 h. Their crystallography, phase transitions, element analysis and nanostructures were investigated by X-ray diffraction, SEM, EDAX and AFM analyses. β-In2S3 phase was dominant and by doping copper impurity, XRD results suggested the formation of CuInS2 compositions. Morphology of the films, nano-structures, grain shapes and hardness was changed. Optical reflectance was measured in the UV-VIS wavelength range by a spectrophotometer. Other optical properties and optical band gaps were calculated using Kramers-Kronig relations on reflectivity curves. Electronic properties were calculated by full potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). In this approach, generalized gradient approximation (GGA) was used for the exchange-correlation potential calculation. Band gap structures, density of states and imaginary parts of dielectric function were calculated for In2S3: Cu compositions.

Segregation at the surfaces of CuxPd1-x alloys in the presence of adsorbed S

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

Miller, James B.; Priyadarshini, Deepika; Gellman, Andrew J.

2012-10-01

The influence of adsorbed S on surface segregation in Cu{sub x}Pd{sub 1 - x} alloys (S/Cu{sub x}Pd{sub 1 - x)} was characterized over a wide range of bulk alloy compositions (x = 0.05 to 0.95) using high-throughput Composition Spread Alloy Film (CSAF) sample libraries. Top-surface and near-surface compositions of the CSAFs were measured as functions of bulk Cu composition, x, and temperature using spatially resolved low energy ion scattering spectroscopy (LEISS) and X-ray photoemission spectroscopy (XPS). Preferential segregation of Cu to the top-surface of the S/Cu{sub x}Pd{sub 1 - x} CSAF was observed at all bulk compositions, x, but themore » extent of Cu segregation to the S/Cu{sub x}Pd{sub 1 - x} surface was lower than the Cu segregation to the surface of a clean Cu{sub x}Pd{sub 1 - x} CSAF, clear evidence of an S-induced “segregation reversal.” The Langmuir–McLean formulation of the Gibbs isotherm was used to estimate the enthalpy and entropy of Cu segregation to the top-surface, ΔH{sub seg}(x) and ΔS{sub seg}(x), at saturation sulfur coverages. While Cu segregation to the top-surface of the clean Cu{sub x}Pd{sub 1 - x} is exothermic (ΔH{sub seg} < 0) for all bulk Cu compositions, it is endothermic (ΔH{sub seg} > 0) for S/Cu{sub x}Pd{sub 1 - x}. Segregation to the S/Cu{sub x}Pd{sub 1 - x} surface is driven by entropy. Changes in segregation patterns that occur upon adsorption of S onto Cu{sub x}Pd{sub 1 - x} appear to be related to formation of energetically favored Pd{single bond}S bonds at the surface, which counterbalance the enthalpic driving forces for Cu segregation to the clean surface.« less

Influence of Asymmetric Cyclic Loading on Structural Evolution and Deformation Behavior of Cu-5 at.% Zr Alloy: An Atomistic Simulation-Based Study

NASA Astrophysics Data System (ADS)

Meraj, Md.; Dutta, Krishna; Bhardwaj, Ravindra; Yedla, Natraj; Karthik, V.; Pal, Snehanshu

2017-11-01

Molecular dynamics (MD) simulation-based studies of tensile test and structural evolution of Cu-5 at.% Zr alloy under asymmetric cyclic loading (i.e., ratcheting behavior) considering various stress ratios such as - 0.2, - 0.4 and - 0.6 for different temperatures, viz.≈ 100, 300 and 500 K have been performed using embedded atom model Finnis-Sinclair potential. According to obtained stress-strain response from MD calculation, Cu-5 at.% Zr alloy specimen is pristine in nature as sudden drop in stress just after yield stress and subsequent elastic type deformation are observed for this alloy. Predicted ratcheting strain by MD simulation for Cu-5 at.% Zr alloy varies from 4.5 to 5%. Significant increase in ratcheting strain has been observed with the increase in temperature. Slight reduction in crystallinity is identified at the middle of the each loading cycle from the performed radial distribution function analysis and cluster analysis.

Fabricated and investigated the structure and super conductivity properties of Bi2Sr2Can-1CunO2n+4+δ compound

NASA Astrophysics Data System (ADS)

Mahdi, Shatha H.; Salim, Faiza M.; Jasim, Kareem Ail; Ali, Mohammed Abdulmuhsin; Ahmed, Saja Amer; Fadhel, Noor Q.

2018-05-01

This paper investigated the influence of Cu-O and Ca-O layers change on the superconductivity properties and crystal structure of Bi2Sr2Can-1CunO2n+4+δ superconductor fabricated via conventional solid state reaction method. X-ray diffraction technique was utilized to study the structure of the specimens. The results showed that a change in the lattice parameters a, b, and c, and lattice ratio c/a appeared as a function of Cu-O and Ca-O layers change, while c/a ratio increased with the increasing of n(of Cu-O and Ca-O layers). However, the electrical resistivity as a function of temperature was used to calculate critical temperature of transition Tc, Tc (offset) = 137k,138k and 139k and Tc(onset)=144k, 160k,161k for n=1,2 and 3 specimens respectively. The study was came to conclusion that the increase in critical temperature was established due to the increase in n (Ca-O and Cu-O layers) of specimens. Atomic force microscopy showed that the Roughness average and root mean square change with the change of n of all specimens.

Effect of high dietary zinc on plasma ceruloplasmin and erythrocyte superoxide dismutase activities in copper-depleted and repleted rats.

PubMed

Panemangalore, M; Bebe, F N

1996-01-01

The effect of moderately high dietary zinc (Zn) on the activities of plasma (PL) ceruloplasmin (CP), and PL and erythrocyte (RBC) copper (Cu), Zn superoxide dismutase (SOD) was determined in weanling rats fed Cu-deficient (DEF; < 1 mg Cu/kg), marginal (MAR; 2 mg Cu/kg), or control (CON; 5 mg Cu/kg) copper diets containing normal or high Zn (HZn; 60 mg/kg) for 4 wk and supplemented with oral Cu (CuS; 5 mg/L) in drinking water for 0, 1, 3, or 7 d. PL Cu decreased (67% compared to CON; p < or = 0.05) in the DEF and increased to control level after 3 d of CuS; increased in the MAR group after 1 d of CuS. HZn reduced overall PL Cu by 27% in all groups, but did not alter the linear increase in PL Cu between 0 and 3 d of Cu S. PL CP activity altered concomitantly with PL Cu levels: The time course of increase in CP activity after 0-3 d of CuS was not influenced by HZn in the diet and CP declined in the DEF group by 92%. There was no correlation between dietary Cu level and PL CP. PL SOD activity decreased by 46% (p < or = .05) in the DEF group, increased to control activity after 1 d of CuS and declined slightly after 7 d; MAR diet did not alter PL SOD. HZn diet increased PL SOD activity in all groups by 150%, reduced activity in the DEF and MAR groups by 65 and 37% and delayed the recovery of PL SOD after CuS. RBC SOD declined in the DEF and MAR groups by 56 and 33% (p < or = 0.05) and did not respond to CuS; HZn diet did not influence RBC SOD activity. These data indicate that moderately high Zn in the diet reduces PL Cu, but not PL CP activity or the recovery of PL Cu or CP activity after oral CuS of Cu-deficient rats, modifies the response of PL SOD to dietary Cu, but does not influence RBC SOD activity.

Kinetics of bulk photo-initiated copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerizations†

PubMed Central

Song, Han Byul; Baranek, Austin; Bowman, Christopher N.

2016-01-01

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ. Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm−2 light exposure at 400–500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)’s catalytic lifetime and the nature of the step-growth polymerization. PMID:27429650

Kinetics of bulk photo-initiated copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations.

PubMed

Song, Han Byul; Baranek, Austin; Bowman, Christopher N

2016-01-21

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ . Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1 st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm -2 light exposure at 400-500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)'s catalytic lifetime and the nature of the step-growth polymerization.

Preparation and Ablating Behavior of FGM used in a Heat Flux Rocket Engine

NASA Astrophysics Data System (ADS)

He, Xiaodong; Han, Jiecai; Zhang, Xinghong

2002-01-01

Functionally Graded Material (FGM) is a new kind of nonhomogeneous materials, which composition varies gradually and continuously from metals to ceramics, thus excellence of both ceramic and metal is brought fully into play. The impetus for the development of FGM was to make thermal barrier materials for space shuttles and structure such as combustion chamber, gas vane, air vane, nose cone, fuel valve sheets and piston crown. There are several main techniques for making FGMs including chemical vapor deposition (CVD), powder metallurgy, plasma spraying and self-propagating high temperate synthesis (SHS). SHS Technology is the process by which condensed phases are produced by self - sustaining exothermic chemical reaction. Demonstrated advantages of SHS as a method for the preparation of materials include higher purity of the products, low energy requirements, and the relative simplicity of the process. SHS is particularly well suited to fabricating FGM. Due to the rapidity of the combustion reaction, the initial arrangement of the constituent in the green body is unchanged during combustion. In this paper, TiB2-Cu FGM and homogeneous cermets have been prepared by combing forced compaction with SHS. The experimental results show that process parameters significantly influence the combustion synthesis procedure of Ti-B-Cu system. Optimal process parameters have been gained for preparing TiB2-Cu FGM and cermets. TiB2-Cu FGM by SHS has a continuous distribution in microstructure along its thickness. The macroscopic interface of ceramic/metal joint is elemented. Mechanical properties of TiB2-Cu cermets were investigated at room and high temperature. The thermal stress of TiC-Ni FGM prepared by SHS are simulated at working condition, as well as comparing with a layered TiB2-Cu Non- FGM. Obviously, the TiB2-Cu FGM has the function of distortion and thermal stress relation. TiB2-Cu FGM was tested in the limited wind tunnel simulating the real condition of the heat flux rocket engine. As a result, TiB2-Cu FGM showed excellent resistant ablating properties. There is only a little loss of the mass after heated for 40 seconds in the wind tunnel. Meanwhile no cracks and breakup appeared in the FGM under the sharp thermal shock condition. Key words: functionally graded materials, combustion synthesis, ablation, thermal shock, thermal stress

A behavioral genetic analysis of callous-unemotional traits and Big Five personality in adolescence.

PubMed

Mann, Frank D; Briley, Daniel A; Tucker-Drob, Elliot M; Harden, K Paige

2015-11-01

Callous-unemotional (CU) traits, such as lacking empathy and emotional insensitivity, predict the onset, severity, and persistence of antisocial behavior. CU traits are heritable, and genetic influences on CU traits contribute to antisocial behavior. This study examines genetic overlap between CU traits and general domains of personality. We measured CU traits using the Inventory of Callous-Unemotional Traits (ICU) and Big Five personality using the Big Five Inventory in a sample of adolescent twins from the Texas Twin Project. Genetic influences on the Big Five personality dimensions could account for the entirety of genetic influences on CU traits. Item Response Theory results indicate that the Inventory of Callous and Unemotional Traits is better at detecting clinically relevant personality variation at lower extremes of personality trait continua, particularly low agreeableness and low conscientiousness. The proximate biological mechanisms that mediate genetic liabilities for CU traits remain an open question. The results of the current study suggest that understanding the development of normal personality may inform understanding of the genetic underpinnings of callous and unemotional behavior. (c) 2015 APA, all rights reserved).

The influence of tumor oxygenation on hypoxia imaging in murine squamous cell carcinoma using [64Cu]Cu-ATSM or [18F]Fluoromisonidazole positron emission tomography.

PubMed

Matsumoto, Ken-Ichiro; Szajek, Lawrence; Krishna, Murali C; Cook, John A; Seidel, Jurgen; Grimes, Kelly; Carson, Joann; Sowers, Anastasia L; English, Sean; Green, Michael V; Bacharach, Stephen L; Eckelman, William C; Mitchell, James B

2007-04-01

[64Cu]Cu(II)-ATSM (64Cu-ATSM) and [18F]-Fluoromisonidazole (18F-FMiso) tumor binding as assessed by positron emisson topography (PET) was used to determine the responsiveness of each probe to modulation in tumor oxygenation levels in the SCCVII tumor model. Animals bearing the SCCVII tumor were injected with 64Cu-ATSM or 18F-FMiso followed by dynamic small animal PET imaging. Animals were imaged with both agents using different inspired oxygen mixtures (air, 10% oxygen, carbogen) which modulated tumor hypoxia as independently assessed by the hypoxia marker pimonidazole. The extent of hypoxia in the SCCVII tumor as monitored by the pimonidazole hypoxia marker was found to be in the following order: 10% oxygen>air>carbogen. Tumor uptake of 64Cu-ATSM could not be changed if the tumor was oxygenated using carbogen inhalation 90 min post-injection suggesting irreversible cellular uptake of the 64Cu-ATSM complex. A small but significant paradoxical increase in 64Cu-ATSM tumor uptake was observed for animals breathing air or carbogen compared to 10% oxygen. There was a positive trend toward 18F-FMiso tumor uptake as a function of changing hypoxia levels in agreement with the pimonidazole data. 64Cu-ATSM tumor uptake was unable to predictably detect changes in varying amounts of hypoxia when oxygenation levels in SCCVII tumors were modulated. 18F-FMiso tumor uptake was more responsive to changing levels of hypoxia. While the mechanism of nitroimidazole binding to hypoxic cells has been extensively studied, the avid binding of Cu-ATSM to tumors may involve other mechanisms independent of hypoxia that warrant further study.

Programmable Modulation of Copper Nanoclusters Electrochemiluminescence via DNA Nanocranes for Ultrasensitive Detection of microRNA.

PubMed

Zhou, Ying; Wang, Haijun; Zhang, Han; Chai, Yaqin; Yuan, Ruo

2018-03-06

The DNA nanocrane with functionalized manipulator and fixed-size base offered a programmable approach to modulate the luminous efficiency of copper nanoclusters (Cu NCs) for achieving remarkable electrochemiluminescence (ECL) enhancement, further the Cu NCs as signal label was constructed in biosensor for ultrasensitive detection of microRNA-155. Herein, the DNA nanocrane was first constructed by combining binding-induced DNA assembly as manipulator and tetrahedral DNA nanostructure (TDN) as base, which harnessed a small quantity of specific target (microRNA (miRNA)-155) binding to trigger assembly of separate DNA components for producing numerous AT-rich double-stranded DNA (dsDNA) on the vertex of TDN. Upon the incubation of Cu 2+ on the AT-rich dsDNA, each DNA-stabilized Cu NCs probe could be in situ electrochemically generated on an individual TDN owing to the A-Cu 2+ -T bond. Thus, the generation of Cu NCs was highly regulated with AT-rich dsDNA as the template, and its lateral distance was tuned by the TDN size, which were two key factors to influence the luminous efficiency of Cu NCs. By coordinate modulation, the detection limit of the ultrasensitive biosensor for miRNA-155 down to 36 aM and the programmable modulation strategy paved the way for comprehensive applications of DNA nanomachines and metal nanoclusters in biosensing and clinical diagnosis.

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

PubMed

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

2015-03-21

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

Chalcogenide thin films deposited by rfMS technique using a single quaternary target

NASA Astrophysics Data System (ADS)

Prepelita, P.; Stavarache, I.; Negrila, C.; Garoi, F.; Craciun, V.

2017-12-01

Thin films of chalcogenide, Cu(In,Ga)Se2 have been obtained using a single quaternary target by radio frequency magnetron sputtering method, with thickness in the range 750 nm to 1200 nm. X-ray photoelectron spectroscopy investigations showed, that the composition of Cu(In,Ga)Se2 thin films was very similar to that of the used target CuIn0.75Ga0.25Se2. Identification of the chemical composition of Cu(In,Ga)Se2 thin films by XPS performed in high vacuum, emphasized that the samples exhibit surface features suitable to be integrated into the structure of solar cells. Atomic Force Microscopy and Scanning Electron Microscopy investigations showed that surface morphology was influenced by the increase in thickness of the Cu(In,Ga)Se2 layer. From X-Ray Diffraction investigations it was found that all films were polycrystalline, having a tetragonal lattice with a preferential orientation along the (112) direction. The optical reflectance as a function of wavelength was measured for the studied samples. The increase in thickness of the Cu(In,Ga)Se2 absorber determined a decrease of its optical bandgap value from 1.53 eV to 1.44 eV. The results presented in this paper showed an excellent alternative of obtaining Cu(In,Ga)Se2 compound thin films from a single target.

Organic zinc and copper supplementation on antioxidant protective mechanism and their correlation with sperm functional characteristics in goats.

PubMed

Narasimhaiah, M; Arunachalam, A; Sellappan, S; Mayasula, V K; Guvvala, P R; Ghosh, S K; Chandra, V; Ghosh, J; Kumar, H

2018-06-01

Trace minerals feeding had significant effects on sperm production and fertility with better absorption and proper utilization within the body for optimum reproductive function. Several studies have shown that more influenced trace elements in the diets of animals are copper (Cu) and zinc (Zn). Bucks showing deficiency of this mineral might affect the quality of semen production which in turn would affect the fertility. This experiment was thus designed to test the effects of organic Cu and Zn supplementation on antioxidants enzyme activities and sperm functional attributes in fresh semen of bucks. Forty bucks (n = 40, Aged 5 months) were assigned to ten groups of four animals in each group, supplemented (for a period of 8 months) with different levels of organic Zn: 20 mg (T2), 40 mg (T3) and 60 mg (T4), organic Cu: 12.5 mg (T5), 25 mg (T6), 37.5 mg (T7) and combined organic Zn and Cu: 20 + 12.5 mg (T8), 40 + 25 mg (T9), 60 + 37.5 mg (T10), respectively, per kg dry matter and no additional mineral diet (control; T1). One hundred and sixty semen samples were collected through electro-ejaculator and analysed for sperm quantity, quality, acrosome intactness and plasma membrane integrity and correlated with the catalase, superoxide dismutase, glutathione peroxidase and glutathione reductase enzyme activities in seminal plasma. The results indicated organic Cu and zinc supplemented bucks produced more sperm cells, had higher sperm concentrations, maintained higher (p < .01) sperm livability, plasma membrane and acrosome integrities, more motility and velocity. The increased antioxidant enzyme activities, reduced oxidative stress and lowered lipid peroxidation were positively correlated (p < .05) with the sperm functional attributes. In conclusion, organic Cu and Zn supplement to male goats showed protective roles against oxidative damage and maintained better fresh semen characteristics. © 2018 Blackwell Verlag GmbH.

Interfacial Reaction and IMC Growth of an Ultrasonically Soldered Cu/SAC305/Cu Structure during Isothermal Aging

PubMed Central

Long, Weifeng; Hu, Xiaowu; Fu, Yanshu

2018-01-01

In order to accelerate the growth of interfacial intermetallic compound (IMC) layers in a soldering structure, Cu/SAC305/Cu was first ultrasonically spot soldered and then subjected to isothermal aging. Relatively short vibration times, i.e., 400 ms and 800 ms, were used for the ultrasonic soldering. The isothermal aging was conducted at 150 °C for 0, 120, 240, and 360 h. The evolution of microstructure, the IMC layer growth mechanism during aging, and the shear strength of the joints after aging were systemically investigated. Results showed the following. (i) Formation of intermetallic compounds was accelerated by ultrasonic cavitation and streaming effects, the thickness of the interfacial Cu6Sn5 layer increased with aging time, and a thin Cu3Sn layer was identified after aging for 360 h. (ii) The growth of the interfacial IMC layer of the ultrasonically soldered Cu/SAC305/Cu joints followed a linear function of the square root of the aging time, revealing a diffusion-controlled mechanism. (iii) The tensile shear strength of the joint decreased to a small extent with increasing aging time, owing to the combined effects of IMC grain coarsening and the increase of the interfacial IMC. (iv) Finally, although the fracture surfaces and failure locations of the joint soldered with 400 ms and 800 ms vibration times show similar characteristics, they are influenced by the aging time. PMID:29316625

The impact of wine components on fractionation of Cu and Fe in model wine systems: Macromolecules, phenolic and sulfur compounds.

PubMed

Kontoudakis, Nikolaos; Smith, Mark; Guo, Anque; Smith, Paul A; Scollary, Geoffrey R; Wilkes, Eric N; Clark, Andrew C

2017-08-01

A variety of techniques have been developed with the ability to measure different forms of metals in wine with the ultimate aim of providing a more accurate indicator of metal induced spoilage of wine. This study was conducted in order to identify which wine components influence the measurement of Cu and Fe in their fractionated and/or electrochemically active forms. The measurement techniques involved detection of labile Cu by stripping potentiometry and fractionation of Cu and Fe by sequential solid phase extraction, with detection by inductively coupled plasma-optical emission spectroscopy. The wine components assessed included those extracted from wine (red wine tannin, white wine protein, white wine polysaccharide, red wine polyphenol, white wine polyphenol), and commercially available monomeric compounds, including phenolic compounds and sulfur-containing compounds. For Cu, only hydrogen sulfide, which is known to induce the formation of Cu(I) sulfide, showed any appreciable influence on the fractionation and electrochemical detection of Cu. This form of Cu was also identified as the major component of red and white wines. For Fe, the fractionation was different for red versus white wine, and influenced significantly by extracted red wine polyphenol, (-)-epicatechin, gallic acid and tartaric acid. The wine components showed more influence on Fe at pH4.00 compared to pH3.25. These results enable a targeted use of these techniques in the assessment of metal-induced spoilage of wine. Copyright © 2016 Elsevier Ltd. All rights reserved.

The characterisation of atomic structure and glass-forming ability of the Zr-Cu-Co metallic glasses studied by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Celtek, M.; Sengul, S.

2018-03-01

In the present work, the glass formation process and structural properties of Zr50Cu50-xCox (0 ≤ x ≤ 50) bulk metallic glasses were investigated by a molecular dynamics simulation with the many body tight-binding potentials. The evolution of structure and glass formation process with temperature were discussed using the coordination number, the radial distribution functions, the volume-temperature curve, icosahedral short-range order, glass transition temperature, Voronoi analysis, Honeycutt-Andersen pair analysis technique and the distribution of bond-angles. Results indicate that adding Co causes similar responses on the nature of the Zr50Cu50-xCox (0 ≤ x ≤ 50) alloys except for higher glass transition temperature and ideal icosahedral type ordered local atomic environment. Also, the differences of the atomic radii play the key role in influencing the atomic structure of these alloys. Both Cu and Co atoms play a significant role in deciding the chemical and topological short-range orders of the Zr50Cu50-xCox ternary liquids and amorphous alloys. The glass-forming ability of these alloys is supported by the experimental observations reported in the literature up to now.

Influence of La content on magnetic properties of Cu doped M-type strontium hexaferrite: Structural, magnetic, and Mossbauer spectroscopy study

NASA Astrophysics Data System (ADS)

Ghimire, M.; Yoon, S.; Wang, L.; Neupane, D.; Alam, J.; Mishra, S. R.

2018-05-01

The present study investigates the influence of Cu2+ and La3+-Cu2+ doping on the magnetic properties of Sr1-xLaxFe12-xCuxO19 (x = 0.0-0.5) hexaferrite (SrM) compounds. The samples were prepared via facile autocombustion technique followed by sintering. X-ray powder diffraction patterns show the formation of the pure phase of M-type hexaferrite for all x. Invariance in lattice parameters was observed with only Cu2+ substitution while lattice contraction along c-axis was observed with co-doping La3+-Cu2+ in SrM. The magnetic property of these compounds is explained based on Cu2+ occupancy in the absence and presence of La3+ in SrM magnetoplumbite structure. The Cu2+ doped SrFe12-xCuxO19 sample showed a monotonic decrease in Ms value while La3+-Cu2+ showed a noticeable increase in Ms value with x. Furthermore, while coercivity of Cu2+ doped SrM reduced with x, the coercivity of La3+-Cu2+ doped SrM showed a marked 12% increase in coercivity at x = 0.1 (Hc = 4391 Oe) from that of x = 0.0 (3918 Oe). Interestingly, Cu2+ doped SrM displayed invariance in Tc ∼ 458.6 °C with x, while La3+-Cu2+ doping reduced Tc by 5% from its x = 0 (Tc = 451.9 °C) to 429.6 °C. The room temperature Mossbauer spectral analysis confirmed a Cu2+ preference for the 12k site and its occupancy is observed to be influenced by the presence of La3+ ion at the Sr2+ site.

Facile and green preparation of novel adsorption materials by combining sol-gel with ion imprinting technology for selective removal of Cu(II) ions from aqueous solution

NASA Astrophysics Data System (ADS)

Ren, Zhongqi; Zhu, Xinyan; Du, Jian; Kong, Delong; Wang, Nian; Wang, Zhuo; Wang, Qi; Liu, Wei; Li, Qunsheng; Zhou, Zhiyong

2018-03-01

A novel green adsorption polymer was prepared by ion imprinted technology in conjunction with sol-gel process under mild conditions for the selective removal of Cu(II) ions from aqueous solution. Effects of preparation conditions on adsorption performance of prepared polymers were studied. The ion-imprinted polymer was prepared using Cu(II) ion as template, N-[3-(2-aminoethylamino) propyl] trimethoxysilane (AAPTMS) as functional monomer and tetraethyl orthosilicate (TEOS) as cross-linker. Water was used as solvent in the whole preparation process. The imprinted and non-imprinted polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM), Brunauer, Emmett and Teller (BET) and zeta potential. Three-dimensional network structure was formed and functional monomer was successfully cross-linked into the network structure of polymers. Effects of adsorption conditions on adsorption performance of prepared polymers were studied too. The pH value is of great influence on adsorption behavior. Adsorption by ion-imprinted polymer was fast (adsorption equilibrium was reached within 60 min). The adsorption capacity of Cu(II) ion-imprinted polymer was always larger than that of non-imprinted polymer. Pseudo-second-order kinetics model and Freundlich isotherm model fitted well with adsorption data. The maximum adsorption capacity of Cu(II) ion-imprinted polymer was 39.82 mg·g-1. However, the preparation conditions used in this work are much milder than those reported in literatures. The Cu(II) ion-imprinted polymer showed high selectivity and relative selectivity coefficients for Pb(II), Ni(II), Cd(II) and Co(II). In addition, the prepared ion-imprinted polymer could be reused several times without significant loss of adsorption capacity.

Serotonin 1B Receptor Gene (HTR1B) Methylation as a Risk Factor for Callous-Unemotional Traits in Antisocial Boys.

PubMed

Moul, Caroline; Dobson-Stone, Carol; Brennan, John; Hawes, David J; Dadds, Mark R

2015-01-01

The serotonin system is thought to play a role in the aetiology of callous-unemotional (CU) traits in children. Previous research identified a functional single nucleotide polymorphism (SNP) from the promoter region of the serotonin 1B receptor gene as being associated with CU traits in boys with antisocial behaviour problems. This research tested the hypothesis that CU traits are associated with reduced methylation of the promoter region of the serotonin 1B receptor gene due to the influence of methylation on gene expression. Participants (N = 117) were boys with antisocial behaviour problems aged 3-16 years referred to University of New South Wales Child Behaviour Research Clinics. Participants volunteered a saliva sample from which the genotype of a SNP from the promoter region of the serotonin 1B receptor gene and the methylation levels of 30 CpG sites from 3 CpG regions surrounding the location of this polymorphism were assayed. Lower levels of serotonin 1B receptor gene methylation were associated with higher levels of CU traits. This relationship, however, was found to be moderated by genotype and carried exclusively by two CpG sites for which levels of methylation were negatively associated with overall methylation levels in this region of the gene. Results provide support to the emerging literature that argues for a genetically-driven system-wide alteration in serotonin function in the aetiology of CU traits. Furthermore, the results suggest that there may be two pathways to CU traits that involve methylation of the serotonin 1B receptor gene; one that is driven by a genotypic risk and another that is associated with risk for generally increased levels of methylation. Future research that aims to replicate and further investigate these results is required.

Fractionation of fulvic acid by iron and aluminum oxides: influence on copper toxicity to Ceriodaphnia dubia

USGS Publications Warehouse

Smith, Kathleen S.; Ranville, James F.; Lesher, Emily K.; Diedrich, Daniel J.; McKnight, Diane M.; Sofield, Ruth M.

2014-01-01

This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on ,i>Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.

Free Energy Calculations of Crystalline Hard Sphere Complexes Using Density Functional Theory

DOE PAGES

Gunawardana, K. G.S.H.; Song, Xueyu

2014-12-22

Recently developed fundamental measure density functional theory (FMT) is used to study binary hard sphere (HS) complexes in crystalline phases. By comparing the excess free energy, pressure and phase diagram, we show that the fundamental measure functional yields good agreements to the available simulation results of AB, AB 2 and AB 13 crystals. Additionally, we use this functional to study the HS models of five binary crystals, Cu 5Zr(C15 b), Cu 51Zr 14(β), Cu 10Zr 7(φ), CuZr(B2) and CuZr 2 (C11 b), which are observed in the Cu-Zr system. The FMT functional gives well behaved minimum for most of themore » hard sphere crystal complexes in the two dimensional Gaussian space, namely a crystalline phase. However, the current version of FMT functional (white Bear) fails to give a stable minimum for the structure Cu 10Zr 7(φ). We argue that the observed solid phases for the HS models of the Cu-Zr system are true thermodynamic stable phases and can be used as a reference system in perturbation calculations.« less

The influence of Cu+ binding to hypoxanthine on stabilization of mismatches involving hypoxanthine and DNA bases: A DFT study.

PubMed

Masoodi, Hamid Reza; Bagheri, Sotoodeh; Ghaderi, Zahra

2018-05-14

In the present work, the influence of Cu + binding to N3- and N7-positions of hypoxanthine on energetic, geometrical and topological properties of hypoxanthine-guanine, hypoxanthine-adenine, hypoxanthine-cytosine, hypoxanthine-thymine and hypoxanthine-hypoxanthine mismatches is theoretically investigated. The calculations, in gas phase, are performed at B3LYP/6-311++G(3df,3pd) level of theory. Unlike the other mispairs, Cu + binding to N3-position of hypoxanthine causes the proton transfer process from enol form of hypoxanthine to imino forms of adenine and cytosine. This process also occurs in all mismatches having enol form of hypoxanthine when Cu + binds to N7-position of hypoxanthine. The mismatches are stabilized by hydrogen bonds. The influence of Cu + on hydrogen bonds is also examined by atoms in molecules (AIM) and natural bond orbital (NBO) analyses.

Influence of Cu Content on the Microstructure and Mechanical Properties of Cr-Cu-N Coatings

PubMed Central

Ding, Ji Cheng; Zhang, Teng Fei; Wan, Zhi Xin; Mei, Hai Juan; Kang, Myung Chang

2018-01-01

The Cr-Cu-N coatings with various Cu contents (0–25.18 (±0.17) at.%) were deposited on Si wafer and stainless steel (SUS 304) substrates in reactive Ar+N2 gas mixture by a hybrid coating system combining pulsed DC and RF magnetron sputtering techniques. The influence of Cu content on the coating composition, microstructure, and mechanical properties was investigated. The microstructure of the coatings was significantly altered by the introduction of Cu. The deposited coatings exhibit solid solution structure with different compositions in all of the samples. Addition of Cu is intensively favored for preferred orientation growth along (200) direction by restricting in (111) direction. With increasing Cu content, the surface and cross-sectional morphology of coatings were changed from triangle cone-shaped, columnar feature to broccoli-like and compact glassy microstructure, respectively. The mechanical properties including the residual stress, nanohardness, and toughness of the coatings were explored on the basis of Cu content. The highest hardness was obtained at the Cu content of 1.49 (±0.10) at.%. PMID:29552269

Influence of Cu Content on the Microstructure and Mechanical Properties of Cr-Cu-N Coatings.

PubMed

Ding, Ji Cheng; Zhang, Teng Fei; Wan, Zhi Xin; Mei, Hai Juan; Kang, Myung Chang; Wang, Qi Min; Kim, Kwang Ho

2018-01-01

The Cr-Cu-N coatings with various Cu contents (0-25.18 (±0.17) at.%) were deposited on Si wafer and stainless steel (SUS 304) substrates in reactive Ar+N 2 gas mixture by a hybrid coating system combining pulsed DC and RF magnetron sputtering techniques. The influence of Cu content on the coating composition, microstructure, and mechanical properties was investigated. The microstructure of the coatings was significantly altered by the introduction of Cu. The deposited coatings exhibit solid solution structure with different compositions in all of the samples. Addition of Cu is intensively favored for preferred orientation growth along (200) direction by restricting in (111) direction. With increasing Cu content, the surface and cross-sectional morphology of coatings were changed from triangle cone-shaped, columnar feature to broccoli-like and compact glassy microstructure, respectively. The mechanical properties including the residual stress, nanohardness, and toughness of the coatings were explored on the basis of Cu content. The highest hardness was obtained at the Cu content of 1.49 (±0.10) at.%.

Modular Assembly of Hierarchically Structured Polymers

NASA Astrophysics Data System (ADS)

Leophairatana, Porakrit

The synthesis of macromolecules with complex yet highly controlled molecular architectures has attracted significant attention in the past few decades due to the growing demand for specialty polymers that possess novel properties. Despite recent efforts, current synthetic routes lack the ability to control several important architectural variables while maintaining low polydispersity index. This dissertation explores a new synthetic scheme for the modular assembly of hierarchically structured polymers (MAHP) that allows virtually any complex polymer to be assembled from a few basic molecular building blocks using a single common coupling chemistry. Complex polymer structures can be assembled from a molecular toolkit consisting of (1) copper-catalyzed azide-alkyne cycloaddition (CuAAC), (2) linear heterobifunctional macromonomers, (3) a branching heterotrifunctional molecule, (4) a protection/deprotection strategy, (5) "click" functional solid substrates, and (6) functional and responsive polymers. This work addresses the different challenges that emerged during the development of this synthetic scheme, and presents strategies to overcome those challenges. Chapter 3 investigates the alkyne-alkyne (i.e. Glaser) coupling side reactions associated with the atom transfer radical polymerization (ATRP) synthesis of alkyne-functional macromonomers, as well as with the CuAAC reaction of alkyne functional building blocks. In typical ATRP synthesis of unprotected alkyne functional polymers, Glaser coupling reactions can significantly compromise the polymer functionality and undermine the success of subsequent click reactions in which the polymers are used. Two strategies are reported that effectively eliminate these coupling reactions: (1) maintaining low temperature post-ATRP upon exposure to air, followed by immediate removal of copper catalyst; and (2) adding excess reducing agents post-ATRP, which prevents the oxidation of Cu(I) catalyst required by the Glaser coupling mechanism. Post-ATRP Glaser coupling was also influenced by the ATRP synthesis ligand used. The order of ligand activity for catalyzing Glaser coupling was: linear bidentate > tridentate > tetradentate. Glaser coupling can also occur for alkynes held under CuAAC reaction conditions but again can be eliminated by adding appropriate reducing agents. With the strategy presented in Chapter 3, alkyne-terminated polymers of high-functionality were produced without the need for alkyne protecting groups. These "click" functional building blocks were employed to investigate the overall efficiency of the CuAAC "click" coupling reactions between alkyne- and azide-terminated macromonomers as discussed in Chapter 4. Quantitative convolution modeling of the entire molecular weight distribution post-CuAAC indicates a CuAAC efficiency of about 94% and an azide substitution efficiency of >99%. However, incomplete functionality of the azide-terminated macromonomer (˜92%) proves to be the largest factor compromising the overall efficacy of the coupling reactions, and is attributed primarily to the loss of bromine functionality during synthesis by ATRP. To address this issue, we discuss in Chapter 6 the development of a new set of molecular building blocks consisting of alkyne functional substrates and heterobifunctional degradable linkers that allow the growth and subsequent detachment of polymers from the solid substrate. Complex polymeric structures are created by progressive cycles of CuAAC and deprotection reactions that add building blocks to the growing polymer chain ends. We demonstrate that these building blocks were completely stable under both CuAAC and deprotection reaction conditions. Since the desired product is covalently bound to the solid surface, the unreacted monomers/macromonomers and by-products (i.e. non-functional building blocks) can be easily separated from the product via removal of the polymer-tethered solid substrate in one step. Chapter 5 discusses how MAHP was employed to prepare a variety of hierarchically structured polymers and copolymers with controlled branching architectures. alpha-azido,o-TIPS-alkyne-heterobifunctional and heterotrifunctional building blocks were first prepared via ATRP and organic synthesis. Preliminary NMR and SEC studies demonstrated that these building blocks all satisfied the criteria necessary for MAHP: (1) the TIPS protecting group is stable during ATRP and CuAAC, (2) the "click" functionality is completely regenerated during the deprotection step, and (3) the CuAAC reaction of branching macromonomers is quantitative (>94%). To demonstrate the concept, poly(n-butyl acrylate)-b-dipolystyrene- b-dipoly(tert-butyl acrylate) penta-block branching copolymacromer was prepared via MAHP and quantitively characterized with SEC and NMR. (Abstract shortened by ProQuest.).

Influence of bioenergy waste biochar on proton- and ligand-promoted release of Pb and Cu in a shooting range soil.

PubMed

Kumarathilaka, Prasanna; Ahmad, Mahtab; Herath, Indika; Mahatantila, Kushani; Athapattu, B C L; Rinklebe, Jörg; Ok, Yong Sik; Usman, Adel; Al-Wabel, Mohammad I; Abduljabbar, Adel; Vithanage, Meththika

2018-06-01

Presence of organic and inorganic acids influences the release rates of trace metals (TMs) bound in contaminated soil systems. This study aimed to investigate the influence of bioenergy waste biochar, derived from Gliricidia sepium (GBC), on the proton and ligand-induced bioavailability of Pb and Cu in a shooting range soil (17,066mg Pb and 1134mg Cu per kg soil) in the presence of inorganic (sulfuric, nitric, and hydrochloric) and organic acids (acetic, citric, and oxalic). Release rates of Pb and Cu in the shooting range soil were determined under different acid concentrations (0.05, 0.1, 0.5, 1, 5, and 10mM) and in the presence/absence of GBC (10% by weight of soil). The dissolution rates of Pb and Cu increased with increasing acid concentrations. Lead was preferentially released (2.79×10 -13 to 8.86×10 -13 molm -2 s -1 ) than Cu (1.07×10 -13 to 1.02×10 -13 molm -2 s -1 ) which could be due to the excessive Pb concentrations in soil. However, the addition of GBC to soil reduced Pb and Cu dissolution rates to a greater extent of 10.0 to 99.5% and 15.6 to 99.5%, respectively, under various acid concentrations. The increased pH in the medium and different adsorption mechanisms, including electrostatic attractions, surface diffusion, ion exchange, precipitation, and complexation could immobilize Pb and Cu released by the proton and ligands in GBC amended soil. Overall, GBC could be utilized as an effective soil amendment to immobilize Pb and Cu in shooting range soil even under the influence of soil acidity. Copyright © 2017. Published by Elsevier B.V.

Impairment in Children with and without ADHD: Contributions from Oppositional Defiant Disorder and Callous-Unemotional Traits

ERIC Educational Resources Information Center

Brammer, Whitney A.; Lee, Steve S.

2012-01-01

Objective: To ascertain the association of childhood ADHD and oppositional defiant disorder (ODD) on functional impairment and to test the moderating influence of callous-unemotional (CU) traits. Method: Ethnically diverse 6- to 9-year-old children with (n = 59) and without (n = 47) ADHD were ascertained using multiple methods (i.e., rating scales…

Ultraviolet optical absorptions of semiconducting copper phosphate glasses

NASA Technical Reports Server (NTRS)

Bae, Byeong-Soo; Weinberg, Michael C.

1993-01-01

Results are presented of a quantitative investigation of the change in UV optical absorption in semiconducting copper phosphate glasses with batch compositions of 40, 50, and 55 percent CuO, as a function of the Cu(2+)/Cu(total) ratio in the glasses for each glass composition. It was found that optical energy gap, E(opt), of copper phosphate glass is a function of both glass composition and Cu(2+)/Cu(total) ratio in the glass. E(opt) increases as the CuO content for fixed Cu(2+)/Cu(total) ratio and the Cu(2+)/Cu(total) ratio for fixed glass composition are reduced.

Influences of S, Se, Te and Po substitutions on structural, electronic and optical properties of hexagonal CuAlO2 using GGA and B3LYP functionals.

PubMed

Liu, Qi-Jun; Jiao, Zhen; Liu, Fu-Sheng; Liu, Zheng-Tang

2016-06-07

The effects of X-doping (X = S, Se, Te and Po) on the structural, electronic and optical properties of hexagonal CuAlO2 were studied using first-principles density functional theory. The calculated results showed the obtained lattice constants to increase with increasing atomic number, and the X-doping to be energetically more favorable under Al-rich conditions. The calculated electronic properties showed decreased bandgaps with increasing atomic number, which was due to the better covalent hybridizations after sulfuration doping. The enhanced covalency was further confirmed by calculating the Mulliken atomic populations and bond populations. The density of states indicated the increase of the contribution to antibonding from the X-p states to be a benefit for p-type conductivity. Moreover, the X-doping induced a red shift of the absorption edge.

High-Density Lipoprotein Cholesterol Level Relates to Working Memory, Immediate and Delayed Cued Recall in Brazilian Older Adults: The Role of Cognitive Reserve.

PubMed

Ihle, Andreas; Gouveia, Élvio R; Gouveia, Bruna R; Freitas, Duarte L; Jurema, Jefferson; Tinôco, Maria A; Kliegel, Matthias

2017-01-01

The present study set out to investigate the relation of the high-density lipoprotein cholesterol (HDL-C) level to cognitive performance and its interplay with key markers of cognitive reserve in a large sample of older adults. We assessed tests of working memory, immediate and delayed cued recall in 701 older adults from Amazonas, Brazil. The HDL-C level was derived from fasting blood samples. In addition, we interviewed individuals on their education, past occupation, and cognitive leisure activity. A critically low HDL-C level (<40 mg/dL) was significantly related to lower performance in working memory, immediate and delayed cued recall. Moderation analyses suggested that the relations of the HDL-C level to working memory and delayed cued recall were negligible in individuals with longer education, a higher cognitive level of the job, and greater engagement in cognitive leisure activity. Cognitive reserve accumulated during the life course may reduce the detrimental influences of a critically low HDL-C level on cognitive functioning in old age. © 2017 S. Karger AG, Basel.

Electro-optical properties of Cu2O for P excitons in the regime of Franz-Keldysh oscillations

NASA Astrophysics Data System (ADS)

Zielińska-Raczyńska, Sylwia; Ziemkiewicz, David; Czajkowski, Gerard

2018-04-01

We present the analytical method which enables one to compute the optical functions i.e., reflectivity, transmission, and absorption, including the excitonic effects, for a semiconductor crystal exposed to a uniform electric field for the energy region above the gap and for the external field suitable for the appearance of Franz-Keldysh (FK) oscillations. Our approach intrinsically takes into account the coherence between the carriers and the electromagnetic field. We quantitatively describe the amplitudes and periodicity of FK modulations as well as the influence of Rydberg excitons on the FK effect. Our analytical findings are illustrated numerically for P excitons in Cu2O crystal.

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.

Thin Cu film resistivity using four probe techniques: Effect of film thickness and geometrical shapes

NASA Astrophysics Data System (ADS)

Choudhary, Sumita; Narula, Rahul; Gangopadhyay, Subhashis

2018-05-01

Precise measurement of electrical sheet resistance and resistivity of metallic thin Cu films may play a significant role in temperature sensing by means of resistivity changes which can further act as a safety measure of various electronic devices during their operation. Four point probes resistivity measurement is a useful approach as it successfully excludes the contact resistance between the probes and film surface of the sample. Although, the resistivity of bulk samples at a particular temperature mostly depends on its materialistic property, however, it may significantly differ in the case of thin films, where the shape and thickness of the sample can significantly influence on it. Depending on the ratio of the film thickness to probe spacing, samples are usually classified in two segments such as (i) thick films or (ii) thin films. Accordingly, the geometric correction factors G can be related to the sample resistivity r, which has been calculated here for thin Cu films of thickness up to few 100 nm. In this study, various rectangular shapes of thin Cu films have been used to determine the shape induced geometric correction factors G. An expressions for G have been obtained as a function of film thickness t versus the probe spacing s. Using these expressions, the correction factors have been plotted separately for each cases as a function of (a) film thickness for fixed linear probe spacing and (b) probe distance from the edge of the film surface for particular thickness. Finally, we compare the experimental results of thin Cu films of various rectangular geometries with the theoretical reported results.

Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

USGS Publications Warehouse

Pribil, M.J.; Wanty, R.B.; Ridley, W.I.; Borrok, D.M.

2010-01-01

An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO42-) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO42- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO42- present in the Cu fraction can form a polyatomic 32S-14N-16O-1H species causing a direct mass interference with 63Cu and producing artificially light ??65Cu values. Here we report the extent of the mass interference caused by SO42- breakthrough when measuring ??65Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO42- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO42- resulted in an average ??65Cu of -3.50?????5.42??? following single anion column separation with variable SO42- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO42-concentration of 13??g/L resulted in better precision and accuracy for the measured ??65Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO42- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ??65Cu and may require the use of a double ion exchange column procedure. ?? 2010.

Influence of moisture content and temperature on degree of carbonation and the effect on Cu and Cr leaching from incineration bottom ash.

PubMed

Lin, Wenlin Yvonne; Heng, Kim Soon; Sun, Xiaolong; Wang, Jing-Yuan

2015-09-01

This study investigated the influence of moisture content and temperature on the degree of carbonation of municipal solid waste (MSW) incineration bottom ash (IBA) from two different incineration plants in Singapore. The initial rate of carbonation was affected by the nominal moisture content used. Carbonation temperature seemed to play a part in changing the actual moisture content of IBA during carbonation, which in turn affected the degree of carbonation. Results showed that 2h of carbonation was sufficient for the samples to reach a relatively high degree of carbonation that was close to the degree of carbonation observed after 1week of carbonation. Both Cu and Cr leaching also showed significant reduction after only 2h of carbonation. Therefore, the optimum moisture content and temperature were selected based on 2h of carbonation. The optimum moisture content was 15% for both incineration plants while the optimum temperature was different for the two incineration plants, at 35°C and 50°C. The effect on Cu and Cr leaching from IBA after accelerated carbonation was evaluated as a function of carbonation time. Correlation coefficient, Pearson's R, was used to determine the dominant leaching mechanism. The reduction in Cu leaching was found to be contributed by both formation of carbonate mineral and reduction of DOC leaching. On the other hand, Cr leaching seemed to be dominantly controlled by pH. Copyright © 2015 Elsevier Ltd. All rights reserved.

Copper and cobalt mobility in soil and accumulation in a metallophyte as influenced by experimental manipulation of soil chemical factors.

PubMed

Lange, Bastien; Pourret, Olivier; Meerts, Pierre; Jitaru, Petru; Cancès, Benjamin; Grison, Claude; Faucon, Michel-Pierre

2016-03-01

The influence of Fe oxides, Mn oxides and organic matter (OM) on the Cu and Co mobility in soil and accumulation in the metallophyte Anisopappus chinensis (Ac), as compared with Helianthus annuus (Ha), was experimentally investigated. Growth and accumulation response when increasing the exchangeable Cu and Co concentrations in soil were also investigated. Plants were cultivated on soil where concentrations of Cu, Co, Fe oxides, Mn oxides and OM content were varied according to 36 treatments. The OM supply decreased the Cu mobility and increased the Co mobility, resulting in decreasing the foliar Cu of Ac and increasing the foliar Co of Ha. The Fe oxides supply could increase the Cu accumulation for Ac, but was not verified for Ha. Compared with Ha, Ac increasingly accumulated Cu and Co without negative effect on plant growth while increasing Cu and Co mobility to phytotoxic concentrations. The results revealed promising perspectives for the use of Ac in Cu-contaminated environment phytoremediation applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluating three trace metal contaminated sites: a field and laboratory investigation.

PubMed

Murray, P; Ge, Y; Hendershot, W H

2000-01-01

Selecting guidelines to evaluate elevated metals in urban brownfields is hindered by the lack of information for these sites on ecosystem structure and function. A study was performed to compare three trace metal-contaminated sites in the metropolitan Montreal area. The goal was to obtain an idea of the organisms that may be present on urban brownfields and to measure if elevated metals alter the presence and activity of the indigenous biota. Field and laboratory studies were conducted using simple methodologies to determine the extent to which microbial activity affected by trace metal content, to assess diversity of plant and soil invertebrate communities and to measure phytoaccumulation of trace metals. It was found that microbial activity, as measured by substrate-induced respiration (SIR) and nitrification, was not affected by the levels of soil Cd, Cu, Ni, Pb and Zn recorded on the sites. Seven of the 12 invertebrate groups collected were sampled on soils with similar Cd, Cu, Ni, Pb and Zn concentrations. Diversity of plant species increased as a function of the length of time the sites had been inactive. Levels of metals in plant tissue were influenced by soil characteristics and not by total soil Cd, Cu, Ni, Pb and Zn.

Nanoscale Stoichiometric Analysis of a High-Temperature Superconductor by Atom Probe Tomography.

PubMed

Pedrazzini, Stella; London, Andrew J; Gault, Baptiste; Saxey, David; Speller, Susannah; Grovenor, Chris R M; Danaie, Mohsen; Moody, Michael P; Edmondson, Philip D; Bagot, Paul A J

2017-04-01

The functional properties of the high-temperature superconductor Y1Ba2Cu3O7-δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y7.7Ba15.3Cu23O54-δ ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of the experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y7.9Ba10.4Cu24.4O57.2.

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

Pedrazzini, Stella; London, Andrew J.; Gault, Baptiste

The functional properties of the high-temperature superconductor Y 1Ba 2Cu 3O 7-δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y 7.7Ba 15.3Cu 23O 54-δ ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of themore » experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y 7.9Ba 10.4Cu 24.4O 57.2.« less

Electron paramagnetic resonance and density-functional theory studies of Cu(II)-bis(oxamato) complexes.

PubMed

Bräuer, Björn; Weigend, Florian; Fittipaldi, Maria; Gatteschi, Dante; Reijerse, Edward J; Guerri, Annalisa; Ciattini, Samuele; Salvan, Georgeta; Rüffer, Tobias

2008-08-04

In this work we present the investigation of the influence of electronic and structural variations induced by varying the N,N'-bridge on the magnetic properties of Cu(II)- bis(oxamato) complexes. For this study the complexes [Cu(opba)] (2-) ( 1, opba = o-phenylene- bis(oxamato)), [Cu(nabo)] (2-) ( 2, nabo = 2,3-naphthalene- bis(oxamato)), [Cu(acbo)] (2-) ( 3, acbo = 2,3-anthrachinone- bis(oxamato)), [Cu(pba)] (2-) ( 4, pba = propylene- bis(oxamato)), [Cu(obbo)] (2-) ( 5, obbo = o-benzyl- bis(oxamato)), and [Cu(npbo)] (2-) ( 6, npbo = 1,8-naphthalene- bis(oxamato)), and the respective structurally isomorphic Ni(II) complexes ( 8- 13) have been prepared as ( (n)Bu 4N) (+) salts. The new complex ( (n)Bu 4N) 2[Cu(R-bnbo)].2H 2O ( 7, R-bnbo = (R)-1,1'-binaphthalene-2,2'- bis(oxamato)) was synthesized and is the first chiral complex in the series of Cu(II)-bis(oxamato) complexes. The molecular structure of 7 has been determined by single crystal X-ray analysis. The Cu(II) ions of the complexes 1- 7 are eta (4)(kappa (2) N, kappa (2) O) coordinated with a more or less distorted square planar geometry for 1- 6 and a distorted tetrahedral geometry for 7. Using pulsed Electron Nuclear Double Resonance on complex 6, detailed information about the relative orientation of the hyperfine ( A) and nuclear quadrupole tensors ( Q) of the coordinating nitrogens with respect to the g tensor were obtained. Electron Paramagnetic Resonance studies in the X, Q, and W-band at variable temperatures were carried out to extract g and A values of N ligands and Cu ion for 1- 7. The hyperfine values were interpreted in terms of spin population on the corresponding atoms. The obtained trends of the spin population for the monomeric building blocks were shown to correlate to the trends obtained in the dependence of the exchange interaction of the corresponding trinuclear complexes on their geometry.

Cannabis use in children and adolescents with first episode psychosis: influence on psychopathology and short-term outcome (CAFEPS study).

PubMed

Baeza, Immaculada; Graell, Montserrat; Moreno, Dolores; Castro-Fornieles, Josefina; Parellada, Mara; González-Pinto, Ana; Payá, Beatriz; Soutullo, César; de la Serna, Elena; Arango, Celso

2009-09-01

To know the prevalence of substance use and its relationship with psychopathology at onset and after six months in children and adolescents with first episode psychosis (FEP). 110 FEP patients, aged 9-17, were assessed for substance use, and with the Positive and Negative Syndrome Scale (PANSS) and other psychopathological and general functioning scales at baseline and after a six-month follow-up. Patients' substance use at baseline was: tobacco (30.9%), cannabis (29.1%), alcohol (21.8%), cocaine (8.2%), amphetamines (2.7%), LSD (1.8%) and opiates (0.90%). Six months later, there was a decrease in patients' use of cannabis (p=0.004) and other drugs, except tobacco. Patients were divided, according to their baseline cannabis use, into 32 cannabis users (CU) and 78 non-cannabis users (NCU). CU were older (p=0.002) and had higher PANSS positive scores (p=0.002) and lower PANSS negative (p<0.001), PANSS general (p=0.002) and PANSS total (p=0.007) scores than NCU. At six months, CU had significantly lower PANSS positive (p=0.010), negative (p=0.0001), general (p=0.002) and total (p=0.002) scores than NCU. When we divided CU at six months into previous CU (n=16) and current CU (n=15), previous CU had the best outcome, NCU the worst and current CU had an intermediate profile. Cannabis use may be related to higher positive symptom scores for FEP patients, with greater improvement after six months for those who cease using cannabis.

Luminescence of ferrocene-modified pyrene derivatives for turn-on sensing of Cu2 + and anions

NASA Astrophysics Data System (ADS)

Sun, Shuhua; Hu, Wenting; Gao, Hongfang; Qi, Honglan; Ding, Liping

2017-09-01

Detection and identification of metal ions by fluorescent turn-on sensors are challenging due to the quenching effect of most of the tested metal ions. In the present work, three ferrocene-modified pyrene-based probes 2-4 were synthesized to act as turn-on fluorescent sensors for Cu2 +. The measurements of fluorescence quantum yield and fluorescence lifetime reveal that ferrocenyl unit can efficiently reduce the fluorescence emission of pyrene moiety. Steady-state fluorescence measurements find that the three ferrocene-modified fluorophores exhibit selective turn-on responses to Cu2 +. Moreover, this turn-on effect to Cu2 + is highly influenced by the type of the counter ion. It is found that the presence of Cl- or NO3- could realize the turn-on response to Cu2 +, whereas, the presence of SO42 - or Ac- could not induce any fluorescence enhancement to Cu2 +. Control experiments with ferrocene-free pyrene-based probe 1 reveal that the ferrocenyl unit plays the key role in the turn-on response to Cu2 +. The possible mechanism for the turn-on responses is attributed to the oxidation behavior of Cu2 + to the ferrocene unit, which is confirmed by the control experiments with sodium ascorbate. Cyclic voltammetry measurements show that Cu2 + can influence the redox behaviors of ferrocenyl derivatives, which is also highly dependent on the anion of the copper salts. The influence of anion on the turn-on responses to Cu2 + was further used for anion detection and fluorescent logic gate.

Luminescence of ferrocene-modified pyrene derivatives for turn-on sensing of Cu2+ and anions.

PubMed

Sun, Shuhua; Hu, Wenting; Gao, Hongfang; Qi, Honglan; Ding, Liping

2017-09-05

Detection and identification of metal ions by fluorescent turn-on sensors are challenging due to the quenching effect of most of the tested metal ions. In the present work, three ferrocene-modified pyrene-based probes 2-4 were synthesized to act as turn-on fluorescent sensors for Cu 2+ . The measurements of fluorescence quantum yield and fluorescence lifetime reveal that ferrocenyl unit can efficiently reduce the fluorescence emission of pyrene moiety. Steady-state fluorescence measurements find that the three ferrocene-modified fluorophores exhibit selective turn-on responses to Cu 2+ . Moreover, this turn-on effect to Cu 2+ is highly influenced by the type of the counter ion. It is found that the presence of Cl - or NO 3 - could realize the turn-on response to Cu 2+ , whereas, the presence of SO 4 2- or Ac - could not induce any fluorescence enhancement to Cu 2+ . Control experiments with ferrocene-free pyrene-based probe 1 reveal that the ferrocenyl unit plays the key role in the turn-on response to Cu 2+ . The possible mechanism for the turn-on responses is attributed to the oxidation behavior of Cu 2+ to the ferrocene unit, which is confirmed by the control experiments with sodium ascorbate. Cyclic voltammetry measurements show that Cu 2+ can influence the redox behaviors of ferrocenyl derivatives, which is also highly dependent on the anion of the copper salts. The influence of anion on the turn-on responses to Cu 2+ was further used for anion detection and fluorescent logic gate. Copyright © 2017 Elsevier B.V. All rights reserved.

Ab initio assessment of Bi1-xRExCuOS (RE = La, Gd, Y, Lu) solid solutions as a semiconductor for photochemical water splitting.

PubMed

Lardhi, Sheikha; Curutchet, Antton; Cavallo, Luigi; Harb, Moussab; Le Bahers, Tangui

2017-05-17

The investigation of the BiCuOCh (Ch = S, Se and Te) semiconductor family for thermoelectric or photovoltaic materials is a topic of increasing research interest. These materials can also be considered for photochemical water splitting if one representative having a bandgap, E g , at around 2 eV can be developed. With this aim, we simulated the solid solutions Bi 1-x RE x CuOS (RE = Y, La, Gd and Lu) from pure BiCuOS (E g ∼ 1.1 eV) to pure RECuOS compositions (E g ∼ 2.9 eV) by DFT calculations based on the HSE06 range-separated hybrid functional with the inclusion of spin-orbit coupling. Starting from the thermodynamic stability of the solid solution, several properties were computed for each system including bandgaps, dielectric constants, effective masses and exciton binding energies. We discussed the variation of these properties based on the relative organization of Bi and RE atoms in their common sublattice to offer a physical understanding of the influence of the RE doping of BiCuOS. Some compositions were found to give appropriate properties for water splitting applications. Furthermore, we found that at low RE fractions the transport properties of BiCuOS are improved that can find applications beyond water splitting.

The antifertility effectiveness of copper/low-density polyethylene nanocomposite and its influence on the endometrial environment in rats.

PubMed

Liu, He-Fang; Liu, Zi-Long; Xie, Chang-Sheng; Yu, Jing; Zhu, Chang-Hong

2007-02-01

The study was conducted to investigate the antifertility effectiveness of copper/low-density polyethylene nanocomposite (nano-Cu/LDPE) and its influence on the endometrial environment in rats. One hundred and seventy sexually mature female Sprague-Dawley (SD) rats were randomly divided into five groups: sham-operated control group (SO group, n=10), bulk copper group (Cu group, n=40), LDPE group (n=40), and nano-Cu/LDPE groups I (n=40) and II (n=40). Twenty rats in each group except for the SO group were mated with male rats of proven fertility, from 30 days after insertion, and the antifertility rates (ATs) were observed at Day 11 of pregnancy. The concentrations of prostaglandin E(2) (PGE(2)) and tissue plasminogen activator (tPA) in the endometrium of the remaining rats in each group were measured by using ELISA at the 30th and 60th day after insertion, respectively. ATs in the Cu group and nano-Cu/LDPE groups I and II (100%) were significantly higher than those in the LDPE group (p<.05). Compared with those in the SO group, the concentrations of PGE(2) and tPA in all experimental groups except for PGE(2) levels in the LDPE group were significantly increased at Day 30 after insertion, and these parameters in the nano-Cu/LDPE groups were significantly lower than in the Cu group (p<.05). At Day 60 after insertion, tPA levels were still higher in the Cu and nano-Cu/LDPE groups, but there was no difference in PGE(2) levels in all groups except for the Cu group. Nano-Cu/LDPE exhibits satisfactory contraceptive efficacy with less influence on the endometrium PGE(2) and tPA levels.

Influence of natural organic matter source on copper speciation as demonstrated by Cu binding to fish gills, by ion selective electrode, and by DGT gel sampler

USGS Publications Warehouse

Luider, C.D.; Crusius, John; Playle, R.C.; Curtis, P.J.

2004-01-01

Rainbow trout (Oncorhynchus mykiss, 2 g) were exposed to 0−5 μM total copper in ion-poor water for 3 h in the presence or absence of 10 mg C/L of qualitatively different natural organic matter (NOM) derived from water spanning a large gradient in hydrologic residence time. Accumulation of Cu by trout gills was compared to Cu speciation determined by ion selective electrode (ISE) and by diffusive gradients in thin films (DGT) gel sampler technology. The presence of NOM decreased Cu uptake by trout gills as well as Cu concentrations determined by ISE and DGT. Furthermore, the source of NOM influenced Cu binding by trout gills with high-color, allochthonous NOM decreasing Cu accumulation by the gills more than low-color autochthonous NOM. The pattern of Cu binding to the NOM measured by Cu ISE and by Cu accumulation by DGT samplers was similar to the fish gill results. A simple Cu−gill binding model required an NOM Cu-binding factor (F) that depended on NOM quality to account for observed Cu accumulation by trout gills; values of F varied by a factor of 2. Thus, NOM metal-binding quality, as well as NOM quantity, are both important when assessing the bioavailability of metals such as Cu to aquatic organisms.

Influence of deposition time on the surface morphology and photoelectrochemical properties of copper doped titania nanotubes prepared by electrodeposition

NASA Astrophysics Data System (ADS)

Mahmud, M. A.; Chin, L. Y.; Khusaimi, Z.; Zainal, Z.

2018-05-01

A great attention has focused on Cu doped titania nanotubes (Cu/TiNT) as a versatile advance material since it can be employed in various promising technological applications. The current study reported on the influence of various deposition times on the surface morphology and photoelectrochemical properties of Cu/TiNT via electrodeposition technique. Cu loaded on the TiNT surface was detected with prolonged deposition time. For photoelectrochemical (PEC) measurement, the highest responsive photocurrent density was obtained at 20 minutes with 54.3 µA/cm2. Too long duration (40 mins) resulted in poor performance of Cu/TiNT as only 22.6 µA/cm2 of photocurrent being generated.

Exogenous attention influences visual short-term memory in infants.

PubMed

Ross-Sheehy, Shannon; Oakes, Lisa M; Luck, Steven J

2011-05-01

Two experiments examined the hypothesis that developing visual attentional mechanisms influence infants' Visual Short-Term Memory (VSTM) in the context of multiple items. Five- and 10-month-old infants (N = 76) received a change detection task in which arrays of three differently colored squares appeared and disappeared. On each trial one square changed color and one square was cued; sometimes the cued item was the changing item, and sometimes the changing item was not the cued item. Ten-month-old infants exhibited enhanced memory for the cued item when the cue was a spatial pre-cue (Experiment 1) and 5-month-old infants exhibited enhanced memory for the cued item when the cue was relative motion (Experiment 2). These results demonstrate for the first time that infants younger than 6 months can encode information in VSTM about individual items in multiple-object arrays, and that attention-directing cues influence both perceptual and VSTM encoding of stimuli in infants as in adults.

Low-dose copper infusion into the coronary circulation induces acute heart failure in diabetic rats: New mechanism of heart disease.

PubMed

Cheung, Carlos Chun Ho; Soon, Choong Yee; Chuang, Chia-Lin; Phillips, Anthony R J; Zhang, Shaoping; Cooper, Garth J S

2015-09-01

Diabetes impairs copper (Cu) regulation, causing elevated serum Cu and urinary Cu excretion in patients with established cardiovascular disease; it also causes cardiomyopathy and chronic cardiac impairment linked to defective Cu homeostasis in rats. However, the mechanisms that link impaired Cu regulation to cardiac dysfunction in diabetes are incompletely understood. Chronic treatment with triethylenetetramine (TETA), a Cu²⁺-selective chelator, improves cardiac function in diabetic patients, and in rats with heart disease; the latter displayed ∼3-fold elevations in free Cu²⁺ in the coronary effluent when TETA was infused into their coronary arteries. To further study the nature of defective cardiac Cu regulation in diabetes, we employed an isolated-perfused, working-heart model in which we infused micromolar doses of Cu²⁺ into the coronary arteries and measured acute effects on cardiac function in diabetic and non-diabetic-control rats. Infusion of CuCl₂ solutions caused acute dose-dependent cardiac dysfunction in normal hearts. Several measures of baseline cardiac function were impaired in diabetic hearts, and these defects were exacerbated by low-micromolar Cu²⁺ infusion. The response to infused Cu²⁺ was augmented in diabetic hearts, which became defective at lower infusion levels and underwent complete pump failure (cardiac output = 0 ml/min) more often (P < 0.0001) at concentrations that only moderately impaired function of control hearts. To our knowledge, this is the first report describing the acute effects on cardiac function of pathophysiological elevations in coronary Cu²⁺. The effects of Cu²⁺ infusion occur within minutes in both control and diabetic hearts, which suggests that they are not due to remodelling. Heightened sensitivity to the acute effects of small elevations in Cu²⁺ could contribute substantively to impaired cardiac function in patients with diabetes and is thus identified as a new mechanism of heart disease. Copyright © 2015 Elsevier Inc. All rights reserved.

Effect of soil parameters on the kinetics of the displacement of Fe from FeEDDHA chelates by Cu.

PubMed

Schenkeveld, Walter D C; Reichwein, Arjen M; Temminghoff, Erwin J M; van Riemsdijk, Willem H

2012-06-28

In soil application, o,o-FeEDDHA (iron (3+) ethylene diamine-N,N'-bis(2-hydroxy phenyl acetic acid) complex) is the active ingredient of FeEDDHA chelate-based Fe fertilizers. The effectiveness of o,o-FeEDDHA is potentially compromised by the displacement of Fe from FeEDDHA by Cu. The actual impact of Cu competition is codetermined by the kinetics of the displacement reaction. In this study, the influence of soil parameters on the displacement kinetics has been examined in goethite suspensions. The displacement reaction predominantly takes place on the reactive surface rather than in solution. The rate at which the o,o-FeEDDHA concentration declined depended on the available reactive surface area, the Cu loading, and the FeEDDHA loading. Soil factors reducing FeEDDHA adsorption (high ionic strength, humic acid adsorption onto the goethite surface, and monovalent instead of divalent cations in the electrolyte) decreased the displacement rate. For meso o,o-FeEDDHA, the displacement rate equation was derived, which is first order in FeEDDHA loading and half order in Cu loading. For soil conditions, the equation can be simplified to an exponential decay function in meso o,o-FeEDDHA solution concentration.

Using response time distributions to examine top-down influences on attentional capture.

PubMed

Burnham, Bryan R

2013-02-01

Three experiments examined contingent attentional capture, which is the finding that cuing effects are larger when cues are perceptually similar to a target than when they are dissimilar to the target. This study also analyzed response times (RTs) in terms of the underlying distributions for valid cues and invalid cues. Specifically, an ex-Gaussian analysis and a vincentile analysis examined the influence of top-down attentional control settings on the shift and skew of RT distributions and how the shift and the skew contributed to the cuing effects in the mean RTs. The results showed that cue/target similarity influenced the size of cuing effects. The RT distribution analyses showed that the cuing effects reflected only a shifting effect, not a skewing effect, in the RT distribution between valid cues and invalid cues. That is, top-down attentional control moderated the cuing effects in the mean RTs through distribution shifting, not distribution skewing. The results support the contingent orienting hypothesis (Folk, Remington, & Johnston, Journal of Experimental Psychology: Human Perception and Performance, 18, 1030-1044, 1992) over the attentional disengagement account (Theeuwes, Atchley, & Kramer, 2000) as an explanation for when top-down attentional settings influence the selection of salient stimuli.

Influence of Al/CuO reactive multilayer films additives on exploding foil initiator

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

Zhou Xiang; Shen Ruiqi; Ye Yinghua

2011-11-01

An investigation on the influence of Al/CuO reactive multilayer films (RMFs) additives on exploding foil initiator was performed in this paper. Cu film and Cu/Al/CuO RMFs were produced by using standard microsystem technology and RF magnetron sputtering technology, respectively. Scanning electron microscopy characterization revealed the distinct layer structure of the as-deposited Al/CuO RMFs. Differential scanning calorimetry was employed to ascertain the amount of heat released in the thermite reaction between Al films and CuO films, which was found to be 2024 J/g. Electrical explosion tests showed that 600 V was the most matching voltage for our set of apparatus. Themore » explosion process of two types of films was observed by high speed camera and revealed that compared with Cu film, an extra distinct combustion phenomenon was detected with large numbers of product particles fiercely ejected to a distance of about six millimeters for Cu/Al/CuO RMFs. By using the atomic emission spectroscopy double line technique, the reaction temperature was determined to be about 6000-7000 K and 8000-9000 K for Cu film and Cu/Al/CuO RMFs, respectively. The piezoelectricity of polyvinylidene fluoride film was employed to measure the average velocity of the slapper accelerated by the explosion of the films. The average velocities of the slappers were calculated to be 381 m/s and 326 m/s for Cu film and Cu/Al/CuO RMFs, respectively, and some probable reasons were discussed with a few suggestions put forward for further work.« less

Influence of Al/CuO reactive multilayer films additives on exploding foil initiator

NASA Astrophysics Data System (ADS)

Zhou, Xiang; Shen, Ruiqi; Ye, Yinghua; Zhu, Peng; Hu, Yan; Wu, Lizhi

2011-11-01

An investigation on the influence of Al/CuO reactive multilayer films (RMFs) additives on exploding foil initiator was performed in this paper. Cu film and Cu/Al/CuO RMFs were produced by using standard microsystem technology and RF magnetron sputtering technology, respectively. Scanning electron microscopy characterization revealed the distinct layer structure of the as-deposited Al/CuO RMFs. Differential scanning calorimetry was employed to ascertain the amount of heat released in the thermite reaction between Al films and CuO films, which was found to be 2024 J/g. Electrical explosion tests showed that 600 V was the most matching voltage for our set of apparatus. The explosion process of two types of films was observed by high speed camera and revealed that compared with Cu film, an extra distinct combustion phenomenon was detected with large numbers of product particles fiercely ejected to a distance of about six millimeters for Cu/Al/CuO RMFs. By using the atomic emission spectroscopy double line technique, the reaction temperature was determined to be about 6000-7000 K and 8000-9000 K for Cu film and Cu/Al/CuO RMFs, respectively. The piezoelectricity of polyvinylidene fluoride film was employed to measure the average velocity of the slapper accelerated by the explosion of the films. The average velocities of the slappers were calculated to be 381 m/s and 326 m/s for Cu film and Cu/Al/CuO RMFs, respectively, and some probable reasons were discussed with a few suggestions put forward for further work.

Shifts in a fish's resource holding power during a contact paired interaction: the influence of a copper-contaminated diet in rainbow trout.

PubMed

Campbell, H A; Handy, R D; Sims, D W

2005-01-01

The influence of sublethal chronic dietary copper (Cu) exposure on the dominant-subordinate relationship between pairs of juvenile rainbow trout (Oncorhynchus mykiss) was examined. Fish were fed either a normal (11 mg Cu kg(-1) food) or Cu-contaminated (721 mg Cu kg(-1) food) diet for 8 wk. Paired interactions were observed--control versus control, Cu-exposed versus Cu-exposed, and control versus Cu-exposed fish--using a computer-aided video tracking system to measure duration of interactions, total distance moved, and the number of encounters during each contest. In concurrence with game theory, each interaction became escalated with a lesser size disparity between contestants. However, in Cu-exposed versus Cu-exposed fish interactions, the dominant-subordinate relationship was decided sooner and with less aggression than a control versus control fish interaction with fish of a similar relative body mass disparity. During control versus Cu-exposed fish interactions, control fish would normally dominate interactions (12 out of 16 bouts) unless the Cu-exposed fish had a 15% body mass advantage. Muscle glycogen and lactate levels after each contest reflected the duration of bouts and winners of the contests, irrespective of Cu exposure. We conclude that Cu-contaminated fish are less able to compete and have lower resource holding power than controls and will withdraw from a contest at a lower level of interaction, unless a size advantage in the Cu-exposed fish increases the probability of winning.

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

PubMed Central

Navarrete, Jesica U.; Borrok, David M.; Viveros, Marian; Ellzey, Joanne T.

2011-01-01

Copper isotopes may prove to be a useful tool for investigating bacteria–metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ65Cu) to investigate Cu–bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5–6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ65Cusolution–solid = δ65Cusolution – δ65Cusolid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to –0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ65Cusolution–solid ranging from ~+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ65Cu of natural waters and soils is probably considerable. PMID:21785492

The effect of the YBCO-PST composite composition on the superconducting carrier concentration determined by microwave studies under high pressure

NASA Astrophysics Data System (ADS)

Krupski, M.; Stankowski, J.; Przybył, S.; Andrzejewski, B.; Kaczmarek, A.; Hilczer, B.; Marfaing, J.; Caranoni, C.

1999-07-01

The effect of hydrostatic pressure ( p<0.6 GPa) on the superconducting critical temperature Tc in YBa 2Cu 3O 7- δ-Pb(Sc 0.5Ta 0.5)O 3 (YBCO-PST) composite is measured by the method of magnetically modulated microwave absorption (MMMA). The Tc dependence on the PST fraction in weight x (0, 0.25, 0.5 and 0.75) is approximated by an inverted parabola function whereas the influence of pressure on Tc is represented by the equation: d Tc/d p=0.61(2)-1.72(6) x. The result may be explained assuming that PST phase in YBCO-PST composite influences the superconducting carrier concentration similar to the chemical substitution in YBa 2Cu 3O 7 [J.J. Neumeier, H.A. Zimmermann, Phys. Rev. B 47 (1993) 8385]. It is suggested that ions from PST diffuse to YBCO cell during the sintering of the composite.

Band structure calculations of CuAlO2, CuGaO2, CuInO2, and CuCrO2 by screened exchange

NASA Astrophysics Data System (ADS)

Gillen, Roland; Robertson, John

2011-07-01

We report density functional theory band structure calculations on the transparent conducting oxides CuAlO2, CuGaO2, CuInO2, and CuCrO2. The use of the hybrid functional screened-exchange local density approximation (sX-LDA) leads to considerably improved electronic properties compared to standard LDA and generalized gradient approximation (GGA) approaches. We show that the resulting electronic band gaps compare well with experimental values and previous quasiparticle calculations, and show the correct trends with respect to the atomic number of the cation (Al, Ga, In). The resulting energetic depths of Cu d and O p levels and the valence-band widths are considerable improvements compared to LDA and GGA and are in good agreement with available x-ray photoelectron spectroscopy data. Lastly, we show the calculated imaginary part of the dielectric function for all four systems.

Screened hybrid functional applied to 3d0→3d8 transition-metal perovskites LaMO3 (M = Sc-Cu): Influence of the exchange mixing parameter on the structural, electronic, and magnetic properties

NASA Astrophysics Data System (ADS)

He, Jiangang; Franchini, Cesare

2012-12-01

We assess the performance of the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional scheme applied to the perovskite family LaMO3 (M = Sc-Cu) and discuss the role of the mixing parameter α [which determines the fraction of exact Hartree-Fock exchange included in the density functional theory (DFT) exchange-correlation functional] on the structural, electronic, and magnetic properties. The physical complexity of this class of compounds, manifested by the largely varying electronic characters (band/Mott-Hubbard/charge-transfer insulators and metals), magnetic orderings, structural distortions (cooperative Jahn-Teller-type instabilities), as well as by the strong competition between localization/delocalization effects associated with the gradual filling of the t2g and eg orbitals, symbolize a critical and challenging case for theory. Our results indicate that HSE is able to provide a consistent picture of the complex physical scenario encountered across the LaMO3 series and significantly improve the standard DFT description. The only exceptions are the correlated paramagnetic metals LaNiO3 and LaCuO3, which are found to be treated better within DFT. By fitting the ground-state properties with respect to α, we have constructed a set of “optimum” values of α from LaScO3 to LaCuO3: it is found that the optimum mixing parameter decreases with increasing filling of the d manifold (LaScO3: 0.25; LaTiO3 and LaVO3: 0.10-0.15; LaCrO3, LaMnO3, and LaFeO3: 0.15; LaCoO3: 0.05; LaNiO3 and LaCuO3: 0). This trend can be nicely correlated with the modulation of the screening and dielectric properties across the LaMO3 series, thus providing a physical justification to the empirical fitting procedure. Finally, we show that by using this set of optimum mixing parameter, HSE predict dielectric constants in very good agreement with the experimental ones.

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

PubMed

Couillard, D; Chartier, M; Mercier, G

1994-01-01

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

Dynamic failure in two-phase materials

DOE PAGES

Fensin, S. J.; Walker, E. K.; Cerreta, E. K.; ...

2015-12-21

Previous experimental research has shown that microstructural features such as interfaces, inclusions, vacancies, and heterogeneities can all act as voidnucleation sites. However, it is not well understood how important these interfaces are to damage evolution and failure as a function of the surrounding parentmaterials. In this work, we present results on three different polycrystallinematerials: (1) Cu, (2) Cu-24 wt. %Ag, and (3) Cu-15 wt. %Nb which were studied to probe the influence of bi-metal interfaces onvoidnucleation and growth. These materials were chosen due to the range of difference in structure and bulk properties between the two phases. The initial resultsmore » suggest that when there are significant differences between the bulk properties (for example: stacking fault energy, melting temperature, etc.) the type of interface between the two parent materials does not principally control the damage nucleation and growth process. Rather, it is the “weaker” material that dictates the dynamic spall strength of the overall two-phase material.« less

Effect of Cu Alloying on S Poisoning of Ni Surfaces and Nanoparticle Morphologies Using Ab-Initio Thermodynamics Calculations.

PubMed

Kim, Ji-Su; Kim, Byung-Kook; Kim, Yeong-Cheol

2015-10-01

We investigated the effect of Cu alloying on S poisoning of Ni surfaces and nanoparticle morphologies using ab-initio thermodynamics calculations. Based on the Cu segregation energy and the S adsorption energy, the surface energy and nanoparticle morphology of pure Ni, pure Cu, and NiCu alloys were evaluated as functions of the chemical potential of S and the surface orientations of (100), (110), and (111). The constructed nanoparticle morphology was varied as a function of chemical potential of S. We find that the Cu added to Ni for NiCu alloys is strongly segregated into the top surface, and increases the S tolerance of the NiCu nanoparticles.

Attention-deficit/hyperactivity disorder and callous-unemotional traits as moderators of conduct problems when examining impairment in emerging adults.

PubMed

Babinski, Dara E; Neely, Kristina A; Kunselman, Allen; Waschbusch, Daniel A

2017-12-01

This study examines attention-deficit/hyperactivity disorder (ADHD) and callous-unemotional (CU) traits as moderators of the association between conduct problems (CP) and young adult functioning. Young adults (n = 283; M age = 20.82 years; 53.4% female), oversampled for attention and behavior problems, provided self-ratings of ADHD, CP, and CU, and adaptive functioning and psychopathology. ADHD and CU simultaneously moderated relationships between CP and family functioning, tobacco use, and internalizing symptoms. In addition, ADHD moderated the relation between CP and job functioning, and main effects of ADHD in the expected direction were found for educational performance and drug use. CU was associated with poorer educational outcomes. Interestingly, no ADHD, CU, or CP effects were observed for reported alcohol use. Our results highlight the importance of considering ADHD and CU in understanding the impact of CP on young adult functioning and psychopathology, and point to the importance of continued work on this topic. Copyright © 2017 Elsevier B.V. All rights reserved.

Peripheral halo-functionalization in [Cu(N^N)(P^P)]+ emitters: influence on the performances of light-emitting electrochemical cells.

PubMed

Brunner, Fabian; Martínez-Sarti, Laura; Keller, Sarah; Pertegás, Antonio; Prescimone, Alessandro; Constable, Edwin C; Bolink, Henk J; Housecroft, Catherine E

2016-09-27

A series of heteroleptic [Cu(N^N)(P^P)][PF 6 ] complexes is described in which P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyridine substituted in the 4-position of the phenyl groups with atom X (N^N = 1 has X = F, 2 has X = Cl, 3 has X = Br, 4 has X = I; the benchmark N^N ligand with X = H is 5). These complexes have been characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses and cyclic voltammetry; representative single crystal structures are also reported. The solution absorption spectra are characterized by high energy bands (arising from ligand-centred transitions) which are red-shifted on going from X = H to X = I, and a broad metal-to-ligand charge transfer band with λ max in the range 387-395 nm. The ten complexes are yellow emitters in solution and yellow or yellow-orange emitters in the solid-state. For a given N^N ligand, the solution photoluminescence (PL) spectra show no significant change on going from [Cu(N^N)(POP)] + to [Cu(N^N)(xantphos)] + ; introducing the iodo-functionality into the N^N domain leads to a red-shift in λ compared to the complexes with the benchmark N^N ligand 5. In the solid state, [Cu(1)(POP)][PF 6 ] and [Cu(1)(xantphos)][PF 6 ] (fluoro-substituent) exhibit the highest PL quantum yields (74 and 25%, respectively) with values of τ 1/2 = 11.1 and 5.8 μs, respectively. Light-emitting electrochemical cells (LECs) with [Cu(N^N)(P^P)][PF 6 ] complexes in the emissive layer have been tested. Using a block-wave pulsed current driving mode, the best performing device employed [Cu(1)(xantphos)] + and this showed a maximum luminance (Lum max ) of 129 cd m -2 and a device lifetime (t 1/2 ) of 54 h; however, the turn-on time (time to reach Lum max ) was 4.1 h. Trends in performance data reveal that the introduction of fluoro-groups is beneficial, but that the incorporation of heavier halo-substituents leads to poor devices, probably due to a detrimental effect on charge transport; LECs with the iodo-functionalized N^N ligand 4 failed to show any electroluminescence after 50 h.

Effect of dissolved organic matter (DOM) of contrasting origins on Cu and Pb speciation and toxicity to Paracentrotus lividus larvae.

PubMed

Sánchez-Marín, Paula; Santos-Echeandía, Juan; Nieto-Cid, Mar; Alvarez-Salgado, Xosé Antón; Beiras, Ricardo

2010-01-31

Water samples of contrasting origin, including natural seawater, two sediment elutriates and sewage-influenced seawater, were collected and obtained to examine the effect of the dissolved organic matter (DOM) present on metal bioavailability. The carbon content (DOC) and the optical properties (absorbance and fluorescence) of the coloured DOM fraction (CDOM) of these materials were determined. Cu and Pb complexation properties were measured by anodic stripping voltammetry (ASV) and the effect of DOM on Cu and Pb bioavailability was studied by means of the Paracentrotus lividus embryo-larval bioassay. Sediment elutriates and sewage-influenced water (1) were enriched 1.4-1.7 times in DOC; (2) absorbed and reemitted more light; and (3) presented higher Cu complexation capacities (L(Cu)) than the natural seawater used for their preparation. L(Cu) varied from 0.08 microM in natural seawater to 0.3 and 0.5 microM in sediment elutriates and sewage-influenced water, respectively. Differences in DOC, CDOM and Cu complexation capacities were reflected in Cu toxicity. DOM enriched samples presented a Cu EC(50) of 0.64 microM, significantly higher than the Cu EC(50) of natural and artificial seawater, which was 0.38 microM. The protecting effect of DOM on Cu toxicity greatly disappeared when the samples were irradiated with high intensity UV-light. Cu toxicity could be successfully predicted considering ASV-labile Cu concentrations in the samples. Pb complexation by DOM was only detected in the DOM-enriched samples and caused little effect on Pb EC(50). This effect was contrary for both elutriates: one elutriate reduced Pb toxicity in comparison with the control artificial seawater, while the other increased it. UV irradiation of the samples caused a marked increase in Pb toxicity, which correlated with the remaining DOC concentration. DOM parameters were related to Cu speciation and toxicity: good correlations were found between DOC and Cu EC(50), while L(Cu) correlated better with the fluorescence of marine humic substances. The present results stress the importance of characterizing not only the amount but also the quality of seawater DOM to better predict ecological effects from total metal concentration data. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

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

Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com; Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id

2015-09-30

One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) andmore » LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.« less

The copper transporter (SLC31A1/CTR1) is expressed in bovine spermatozoa and oocytes: Copper in IVF medium improves sperm quality.

PubMed

Anchordoquy, J P; Anchordoquy, J M; Pascua, A M; Nikoloff, N; Peral-García, P; Furnus, C C

2017-07-15

Adequate dietary intake of copper (Cu) is required for normal reproductive performance in cattle. The objective of this study was to investigate the pregnancy rates from cattle with deficient, marginal and adequate Cu plasma concentration at the beginning of artificial insemination protocol. Moreover, we determined Cu concentrations present in bovine oviductal fluid (OF), and the effects of Cu on fertilizing ability of bovine spermatozoa. Also, the presence of Cu transporter, SLC31A1 (also known as CTR1), in spermatozoa and in vitro matured oocyte were investigated. We found no differences in pregnancy rates among animals with adequate, marginal, and deficient Cu concentrations measured in plasma at the beginning of fixed-time artificial insemination (FTAI) protocol. Copper concentrations in OF were 38.3 ± 2.17 μg/dL (mean ± SEM) regardless of cupremia levels. The addition of 40 μg/dL Cu to IVF medium enhanced total and progressive motility, sperm viability, functional sperm membrane integrity (HOST), sperm-zona binding, and pronuclear formation. On the other hand, the presence of Cu in IVF medium did not modify acrosome integrity and cleavage rates after IVF, but impaired blastocyst rates. Cu transporter SLC31A1 was detected in bovine spermatozoa in the apical segment of acrosome, and in the oocyte matured in vitro. In conclusion, the results obtained in the present study determined that cupremia levels at the beginning of FTAI protocol did not influence the pregnancy rates at 60 d after insemination. The presence of CTR1 in bovine mature oocyte and spermatozoa, as well as the beneficial effect of Cu on sperm quality would suggest an important role of this mineral during the fertilization process. Copyright © 2017 Elsevier Inc. All rights reserved.

Impact of Annealing Prior to Solution Treatment on Aging Precipitates and Intergranular Corrosion Behavior of Al-Cu-Li Alloy 2050

NASA Astrophysics Data System (ADS)

Ye, Zhi-hao; Cai, Wen-xin; Li, Jin-feng; Chen, Xiang-rong; Zhang, Rui-feng; Birbilis, Nick; Chen, Yong-lai; Zhang, Xu-hu; Ma, Peng-cheng; Zheng, Zi-qiao

2018-06-01

The influences of annealing prior to solution treatment on the grain structure, subsequent aging precipitates, and intergranular corrosion (IGC) of Al-Cu-Li alloy (AA2050) sheet with T6 aging at 448 K (175 °C) were investigated. Annealing impedes the full recrystallization during solution treatment, increasing the population density of T1 (Al2CuLi) precipitates, but decreasing that of θ' (Al2Cu) precipitates, of the aged alloy. Meanwhile, annealing leads to the heterogeneous distribution of T1 precipitates, increasing the alloy hardness, and decreasing the open-circuit potential of the aged alloy. With prolonged aging time, the corrosion mode of the aged AA2050 samples with and without annealing evolved in a similar manner. The corrosion mode as a function of aging may be summarized as local IGC with pitting and general IGC with pitting (following initial aging and under the underaged condition), pitting corrosion (later in the under-aging stage), pitting with slight IGC (near the peak-aged condition), and pitting with local IGC (under the overaging condition). The annealing treatment hinders IGC propagation on the rolling surface while accelerating the IGC on transverse surfaces.

Impact of Annealing Prior to Solution Treatment on Aging Precipitates and Intergranular Corrosion Behavior of Al-Cu-Li Alloy 2050

NASA Astrophysics Data System (ADS)

Ye, Zhi-hao; Cai, Wen-xin; Li, Jin-feng; Chen, Xiang-rong; Zhang, Rui-feng; Birbilis, Nick; Chen, Yong-lai; Zhang, Xu-hu; Ma, Peng-cheng; Zheng, Zi-qiao

2018-04-01

The influences of annealing prior to solution treatment on the grain structure, subsequent aging precipitates, and intergranular corrosion (IGC) of Al-Cu-Li alloy (AA2050) sheet with T6 aging at 448 K (175 °C) were investigated. Annealing impedes the full recrystallization during solution treatment, increasing the population density of T1 (Al2CuLi) precipitates, but decreasing that of θ' (Al2Cu) precipitates, of the aged alloy. Meanwhile, annealing leads to the heterogeneous distribution of T1 precipitates, increasing the alloy hardness, and decreasing the open-circuit potential of the aged alloy. With prolonged aging time, the corrosion mode of the aged AA2050 samples with and without annealing evolved in a similar manner. The corrosion mode as a function of aging may be summarized as local IGC with pitting and general IGC with pitting (following initial aging and under the underaged condition), pitting corrosion (later in the under-aging stage), pitting with slight IGC (near the peak-aged condition), and pitting with local IGC (under the overaging condition). The annealing treatment hinders IGC propagation on the rolling surface while accelerating the IGC on transverse surfaces.

Radio-Frequency-Based NH3-Selective Catalytic Reduction Catalyst Control: Studies on Temperature Dependency and Humidity Influences

PubMed Central

Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

2017-01-01

The upcoming more stringent automotive emission legislations and current developments have promoted new technologies for more precise and reliable catalyst control. For this purpose, radio-frequency-based (RF) catalyst state determination offers the only approach for directly measuring the NH3 loading on selective catalytic reduction (SCR) catalysts and the state of other catalysts and filter systems. Recently, the ability of this technique to directly control the urea dosing on a current NH3 storing zeolite catalyst has been demonstrated on an engine dynamometer for the first time and this paper continues that work. Therefore, a well-known serial-type and zeolite-based SCR catalyst (Cu-SSZ-13) was investigated under deliberately chosen high space velocities. At first, the full functionality of the RF system with Cu-SSZ-13 as sample was tested successfully. By direct RF-based NH3 storage control, the influence of the storage degree on the catalyst performance, i.e., on NOx conversion and NH3 slip, was investigated in a temperature range between 250 and 400 °C. For each operation point, an ideal and a critical NH3 storage degree was found and analyzed in the whole temperature range. Based on the data of all experimental runs, temperature dependent calibration functions were developed as a basis for upcoming tests under transient conditions. Additionally, the influence of exhaust humidity was observed with special focus on cold start water and its effects to the RF signals. PMID:28704929

Radio-Frequency-Based NH₃-Selective Catalytic Reduction Catalyst Control: Studies on Temperature Dependency and Humidity Influences.

PubMed

Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

2017-07-12

The upcoming more stringent automotive emission legislations and current developments have promoted new technologies for more precise and reliable catalyst control. For this purpose, radio-frequency-based (RF) catalyst state determination offers the only approach for directly measuring the NH₃ loading on selective catalytic reduction (SCR) catalysts and the state of other catalysts and filter systems. Recently, the ability of this technique to directly control the urea dosing on a current NH₃ storing zeolite catalyst has been demonstrated on an engine dynamometer for the first time and this paper continues that work. Therefore, a well-known serial-type and zeolite-based SCR catalyst (Cu-SSZ-13) was investigated under deliberately chosen high space velocities. At first, the full functionality of the RF system with Cu-SSZ-13 as sample was tested successfully. By direct RF-based NH₃ storage control, the influence of the storage degree on the catalyst performance, i.e., on NO x conversion and NH₃ slip, was investigated in a temperature range between 250 and 400 °C. For each operation point, an ideal and a critical NH₃ storage degree was found and analyzed in the whole temperature range. Based on the data of all experimental runs, temperature dependent calibration functions were developed as a basis for upcoming tests under transient conditions. Additionally, the influence of exhaust humidity was observed with special focus on cold start water and its effects to the RF signals.

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

PubMed Central

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

2016-01-01

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

Factors affecting the presence of dissolved glutathione in estuarine waters.

PubMed

Tang, Degui; Shafer, Martin M; Karner, Dawn A; Overdier, Joel; Armstrong, David E

2004-08-15

We investigated factors influencing the presence of the thiol glutathione (GSH) in estuarine waters. Our study addressed thiol phase-association, the biological release from algal cultures, and the role of copper in both thiol release and preservation. Our measurements in three diverse estuaries in the continental United States (San Diego Bay, Cape Fear Estuary, and Norfolk Estuary) show that dissolved GSH, present at sub-nanomolar levels, is preferentially partitioned into the ultra-filtrate fraction (<1 kDa) in comparison with dissolved organic carbon (DOC). Concentrations of GSH generally increased with increases in total copper (Cu)levels, although large variability was observed among estuaries. In 30-h exposure experiments, release of dissolved GSH from the diatom Thalassiosira weissflogii into organic ligand-free experimental media was a strong function of added Cu concentration. The released GSH increased from about 0.02 to 0.27 fmol/cell as Cu was increased from the background level (0.5 nM) to 310 nM in the modified Aquil media. However, excretion of GSH was lower (up to 0.13 fmol/cell) when cells were grown in surface waters of San Diego Bay, despite much higher total Cu concentrations. Experiments conducted in-situ in San Diego Bay water indicated that high concentrations of added Cu destabilized GSH, while both Mn(II) and natural colloids promoted GSH stability. In contrast, laboratory experiments in synthetic media indicated that moderate levels of added Cu enhanced GSH stability.

Halo and Pseudohalo Cu(I)-Pyridinato Double Chains with Tunable Physical Properties.

PubMed

Hassanein, K; Amo-Ochoa, P; Gómez-García, C J; Delgado, S; Castillo, O; Ocón, P; Martínez, J I; Perles, J; Zamora, F

2015-11-16

The properties recently reported on the Cu(I)-iodide pyrimidine nonporous 1D-coordination polymer [CuI(ANP)]n (ANP = 2-amino-5-nitropyridine) showing reversible physically and chemically driven electrical response have prompted us to carry a comparative study with the series of [CuX(ANP)]n (X = Cl (1), X = Br (2), X = CN (4), and X = SCN (5)) in order to understand the potential influence of the halide and pseudohalide bridging ligands on the physical properties and their electrical response to vapors of these materials. The structural characterization of the series shows a common feature, the presence of -X-Cu(ANP)-X- (X = Cl, Br, I, SCN) double chain structure. Complex [Cu(ANP)(CN)]n (4) presents a helical single chain. Additionally, the chains show supramolecular interlinked interactions via hydrogen bonding giving rise to the formation of extended networks. Their luminescent and electrical properties have been studied. The results obtained have been correlated with structural changes. Furthermore, the experimental and theoretical results have been compared using the density functional theory (DFT). The electrical response of the materials has been evaluated in the presence of vapors of diethyl ether, dimethyl methylphosphonate (DMMP), CH2Cl2, HAcO, MeOH, and EtOH, to build up simple prototype devices for gas detectors. Selectivity toward gases consisting of molecules with H-bonding donor or acceptor groups is clearly observed. This selective molecular recognition is likely due to the 2-amino-5-nitropyridine terminal ligand.

Adsorption mechanisms of removing heavy metals and dyes from aqueous solution using date pits solid adsorbent.

PubMed

Al-Ghouti, Mohammad A; Li, Juiki; Salamh, Yousef; Al-Laqtah, Nasir; Walker, Gavin; Ahmad, Mohammad N M

2010-04-15

A potential usefulness of raw date pits as an inexpensive solid adsorbent for methylene blue (MB), copper ion (Cu(2+)), and cadmium ion (Cd(2+)) has been demonstrated in this work. This work was conducted to provide fundamental information from the study of equilibrium adsorption isotherms and to investigate the adsorption mechanisms in the adsorption of MB, Cu(2+), and Cd(2+) onto raw date pits. The fit of two models, namely Langmuir and Freundlich models, to experimental data obtained from the adsorption isotherms was checked. The adsorption capacities of the raw date pits towards MB and both Cu(2+) and Cd(2+) ions obtained from Langmuir and Freundlich models were found to be 277.8, 35.9, and 39.5 mg g(-1), respectively. Surface functional groups on the raw date pits surface substantially influence the adsorption characteristics of MB, Cu(2+), and Cd(2+) onto the raw date pits. The Fourier transform infrared spectroscopy (FTIR) studies show clear differences in both absorbances and shapes of the bands and in their locations before and after solute adsorption. Two mechanisms were observed for MB adsorption, hydrogen bonding and electrostatic attraction, while other mechanisms were observed for Cu(2+) and Cd(2+). For Cu(2+), binding two cellulose/lignin units together is the predominant mechanism. For Cd(2+), the predominant mechanism is by binding itself using two hydroxyl groups in the cellulose/lignin unit. 2009 Elsevier B.V. All rights reserved.

Executive function and attention are preserved in older surgically menopausal monkeys receiving estrogen or estrogen plus progesterone.

PubMed

Voytko, Mary Lou; Murray, Rhonda; Higgs, Casey J

2009-08-19

Animal models of menopause have been used to further define the cognitive processes that respond to hormone therapy and to investigate parameters that may influence the cognitive effects of estrogen. Many investigations in animals have focused on memory; however, the effects of hormone therapy on executive function and attention processes have not been well studied. Thus, the purpose of this set of investigations was to assess the effects of estrogen therapy alone or with progesterone on executive and attention processes in middle-aged ovariectomized monkeys. Monkeys were preoperatively trained on a modified version of the Wisconsin card sort task and on a visual cued reaction time task. Hormone therapy was initiated at the time of ovariectomy and cognitive function was reassessed at 2, 12, and 24 weeks postoperatively. Relative to monkeys receiving either of the estrogen therapies, monkeys receiving placebo were impaired in their ability to shift a cognitive set in the Wisconsin card sort task and were impaired in shifting visuospatial attention in the visual cued reaction time task. Our findings are consistent with clinical studies that indicate that hormone therapy can improve executive function and attention processes in postmenopausal women.

Distilling Heterogeneity among Children with Disruptive Behavior: Associations between Symptom Patterns and Social Functioning.

PubMed

Aitken, Madison; Henry, Shanelle; Andrade, Brendan F

2017-10-16

Children with disruptive behavior (DB) are a heterogeneous group who exhibit several characteristics that may contribute to poor social functioning. The present study identified profiles of reactive aggression, proactive aggression, callous-unemotional (CU) traits, and prosocial behavior in a sample of children with DB. Associations with social functioning (social interaction, social status) were then examined, along with sex differences in profile membership. Parent ratings of 304 clinic-referred children ages 6-12 years with DB were analyzed using latent profile analysis. Five profiles were identified: 1) Moderate prosocial behavior, reactive aggression, and CU, and low proactive aggression (labelled Moderate); 2) Relatively high prosocial behavior and low reactive and proactive aggression and CU traits (Prosocial); 3) High prosocial behavior and reactive aggression, moderate proactive aggression, and low-moderate CU (Reactive-Prosocial); 4) Low prosocial behavior, high CU, high-moderate reactive aggression, and low-moderate proactive aggression (Reactive-CU); and 5) Low prosocial behavior and high reactive and proactive aggression and CU (Aggressive-CU). Profiles characterized by CU traits, reactive aggression, and low prosocial behavior were associated with the most problematic parent-rated social interaction and social status. The results highlight the need to differentiate profiles of psychopathology in children with DB to better address factors most associated with social functioning.

An Assessment of Binary Metallic Glasses: Correlations Between Structure, Glass Forming Ability and Stability (Preprint)

DTIC Science & Technology

2011-07-01

comparisons for the combined influence of R, Fα and chemistry, the Cu- Zr , Zr - Cu, Ni- Zr , Zr -Ni, Cu-Hf, Hf-Cu, Zr -Be and Ni- Nb systems are considered. These... Zr and Cu-Hf have R ≈ 1.248 for ខ> structures; Ni- Nb represents ᝿> structures with R ≈ 1.116 and Zr -Be has a radius ratio near R* = 0.710 for a...similar fits, with regression coefficients from 0.66 to 0.93. The limited data for Cu- Hf, Hf-Cu and Ni- Nb fit within the scatter shown for the Cu- Zr

Influences on copper bioaccumulation, growth, and survival of the midge, Chironomus tentans, in metal-contaminated sediments

USGS Publications Warehouse

Besser, John M.; Kubitz, Jody A.; Ingersoll, Chris G.; Braselton, W. Emmett; Giesy, John P.

1995-01-01

Sediment bioassays with larvae of the midge, Chironomus tentans, were used to evaluate influences on the bioavailability and toxicity of copper (Cu) in sediments with a wide range of concentrations of metals, acid-volatile sulfide (AVS), and other physicochemical characteristics. Sediments were collected from sixteen lakes in Michigan, USA, and from twelve sites in the Clark Fork River drainage of Montana, USA, which are contaminated with metals from mining activities and from other anthropogenic sources. Bioassays with C. tentans larvae were conducted for ten days in a static-renewal test system, with endpoints of survival, growth, and metal bioaccumulation. Bioaccumulation of copper (Cu) was strongly correlated with Cu concentrations in porewater, and was increased significantly at Cu concentrations less than those affecting growth or survival. Midge survival and growth were not significantly correlated with concentrations of Cu in sediment or porewater, and were poorly predicted by ratios of acid-extractable metals to AVS in sediments. Principal components analysis indicated that Cu concentrations in porewater and bioaccumulation of Cu by midge larvae were influenced by AVS, sediment organic carbon, and porewater pH, and that toxicity was associated with high concentrations of Cu, high concentrations of zinc (Zn) and ammonia. No toxicity was observed in several sediments which contained low concentrations of AVS and high concentrations of Cu and Zn. In sediments which contain little AVS, bioavailability of metals may be controlled by constituents other than sulfides, such as organic matter and metal hydrous oxides. These results indicate that assessments of toxicity in metal-contaminated sediments should evaluate the importance of metal-binding phases other than sulfides, and the possible contributions of ammonia or other toxicants to toxicity in sediment bioassays.

Influence of flow-through and renewal exposures on the toxicity of copper to rainbow trout

USGS Publications Warehouse

Welsh, P.G.; Lipton, J.; Mebane, C.A.; Marr, J.C.A.

2008-01-01

We examined changes in water chemistry and copper (Cu) toxicity in three paired renewal and flow-through acute bioassays with rainbow trout (Oncorhynchus mykiss). Test exposure methodology influenced both exposure water chemistry and measured Cu toxicity. Ammonia and organic carbon concentrations were higher and the fraction of dissolved Cu lower in renewal tests than in paired flow-through tests. Cu toxicity was also lower in renewal tests; 96 h dissolved Cu LC50 values were 7-60% higher than LC50s from matching flow-through tests. LC50 values in both types of tests were related to dissolved organic carbon (DOC) concentrations in exposure tanks. Increases in organic carbon concentrations in renewal tests were associated with reduced Cu toxicity, likely as a result of the lower bioavailability of Cu-organic carbon complexes. The biotic ligand model of acute Cu toxicity tended to underpredict toxicity in the presence of DOC. Model fits between predicted and observed toxicity were improved by assuming that only 50% of the measured DOC was reactive, and that this reactive fraction was present as fulvic acid. ?? 2007 Elsevier Inc. All rights reserved.

Laboratory investigation of the microbiologically influenced corrosion (MIC) resistance of a novel Cu-bearing 2205 duplex stainless steel in the presence of an aerobic marine Pseudomonas aeruginosa biofilm.

PubMed

Xia, Jin; Yang, Chunguang; Xu, Dake; Sun, Da; Nan, Li; Sun, Ziqing; Li, Qi; Gu, Tingyue; Yang, Ke

2015-01-01

The microbiologically influenced corrosion (MIC) resistance of a novel Cu-bearing 2205 duplex stainless steel (2205 Cu-DSS) against an aerobic marine Pseudomonas aeruginosa biofilm was investigated. The electrochemical test results showed that Rp increased and icorr decreased sharply after long-term immersion in the inoculation medium, suggesting that 2205 Cu-DSS possessed excellent MIC resistance to the P. aeruginosa biofilm. Fluorescence microscope images showed that 2205 Cu-DSS possessed a strong antibacterial ability, and its antibacterial efficiency after one and seven days was 7.75% and 96.92%, respectively. The pit morphology comparison after 14 days between 2205 DSS and 2205 Cu-DSS demonstrated that the latter showed a considerably reduced maximum MIC pit depth compared with the former (1.44 μm vs 9.50 μm). The experimental results suggest that inhibition of the biofilm was caused by the copper ions released from the 2205 Cu-DSS, leading to its effective mitigation of MIC by P. aeruginosa.

Nano-scale stoichiometry analysis of a high temperature superconductor by atom probe tomography

DOE PAGES

Pedrazzini, Stella; London, Andrew J.; Gault, Baptiste; ...

2017-01-31

The functional properties of the high-temperature superconductor Y 1Ba 2Cu 3O 7-δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y 7.7Ba 15.3Cu 23O 54-δ ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of themore » experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y 7.9Ba 10.4Cu 24.4O 57.2.« less

Binuclear Cu A formation in biosynthetic models of Cu A in azurin proceeds via a novel Cu(Cys) 2His mononuclear copper intermediate

DOE PAGES

Chakraborty, Saumen; Polen, Michael J.; Chacon, Kelly N.; ...

2015-09-09

Cu A is a binuclear electron transfer (ET) center found in cytochrome c oxidases (C cOs), nitrous oxide reductases (N 2ORs), and nitric oxide reductase (NOR). In these proteins, the Cu A centers facilitate efficient ET ( k ET > 10 4 s –1) under low thermodynamic driving forces (10–90 mV). While the structure and functional properties of Cu A are well understood, a detailed mechanism of the incorporation of copper into the protein and the identity of the intermediates formed during the Cu A maturation process are still lacking. Previous studies of the Cu A assembly mechanism in vitromore » using a biosynthetic model Cu A center in azurin (Cu AAz) identified a novel intermediate X (I x) during reconstitution of the binuclear site. However, because of the instability of I x and the coexistence of other Cu centers, such as Cu A' and type 1 copper centers, the identity of this intermediate could not be established. In this paper, we report the mechanism of Cu A assembly using variants of Glu114XCu AAz (X = Gly, Ala, Leu, or Gln), the backbone carbonyl of which acts as a ligand to the Cu A site, with a major focus on characterization of the novel intermediate I x. We show that Cu A assembly in these variants proceeds through several types of Cu centers, such as mononuclear red type 2 Cu, the novel intermediate I x, and blue type 1 Cu. Our results show that the backbone flexibility of the Glu114 residue is an important factor in determining the rates of T2Cu → I x formation, suggesting that Cu A formation is facilitated by swinging of the ligand loop, which internalizes the T2Cu capture complex to the protein interior. The kinetic data further suggest that the nature of the Glu114 side chain influences the time scales on which these intermediates are formed, the wavelengths of the absorption peaks, and how cleanly one intermediate is converted to another. Through careful understanding of these mechanisms and optimization of the conditions, we have obtained I x in ~80–85% population in these variants, which allowed us to employ ultraviolet–visible, electron paramagnetic resonance, and extended X-ray absorption fine structure spectroscopic techniques to identify the I x as a mononuclear Cu(Cys) 2(His) complex. Finally, because some of the intermediates have been proposed to be involved in the assembly of native Cu A, these results shed light on the structural features of the important intermediates and mechanism of Cu A formation.« less

Cu-doped ZnO nanorod arrays: the effects of copper precursor and concentration

PubMed Central

2014-01-01

Cu-doped ZnO nanorods have been grown at 90°C for 90 min onto a quartz substrate pre-coated with a ZnO seed layer using a hydrothermal method. The influence of copper (Cu) precursor and concentration on the structural, morphological, and optical properties of ZnO nanorods was investigated. X-ray diffraction analysis revealed that the nanorods grown are highly crystalline with a hexagonal wurtzite crystal structure grown along the c-axis. The lattice strain is found to be compressive for all samples, where a minimum compressive strain of −0.114% was obtained when 1 at.% Cu was added from Cu(NO3)2. Scanning electron microscopy was used to investigate morphologies and the diameters of the grown nanorods. The morphological properties of the Cu-doped ZnO nanorods were influenced significantly by the presence of Cu impurities. Near-band edge (NBE) and a broad blue-green emission bands at around 378 and 545 nm, respectively, were observed in the photoluminescence spectra for all samples. The transmittance characteristics showed a slight increase in the visible range, where the total transmittance increased from approximately 80% for the nanorods doped with Cu(CH3COO)2 to approximately 90% for the nanorods that were doped with Cu(NO3)2. PMID:24855460

The synthetic evaluation of CuO-MnOx-modified pinecone biochar for simultaneous removal formaldehyde and elemental mercury from simulated flue gas.

PubMed

Yi, Yaoyao; Li, Caiting; Zhao, Lingkui; Du, Xueyu; Gao, Lei; Chen, Jiaqiang; Zhai, Yunbo; Zeng, Guangming

2018-02-01

A series of low-cost Cu-Mn-mixed oxides supported on biochar (CuMn/HBC) synthesized by an impregnation method were applied to study the simultaneous removal of formaldehyde (HCHO) and elemental mercury (Hg 0 ) at 100-300° C from simulated flue gas. The metal loading value, Cu/Mn molar ratio, flue gas components, reaction mechanism, and interrelationship between HCHO removal and Hg 0 removal were also investigated. Results suggested that 12%CuMn/HBC showed the highest removal efficiency of HCHO and Hg 0 at 175° C corresponding to 89%and 83%, respectively. The addition of NO and SO 2 exhibited inhibitive influence on HCHO removal. For the removal of Hg 0 , NO showed slightly positive influence and SO 2 had an inhibitive effect. Meanwhile, O 2 had positive impact on the removal of HCHO and Hg 0 . The samples were characterized by SEM, XRD, BET, XPS, ICP-AES, FTIR, and H 2 -TPR. The sample characterization illustrated that CuMn/HBC possessed the high pore volume and specific surface area. The chemisorbed oxygen (O β ) and the lattice oxygen (O α ) which took part in the removal reaction largely existed in CuMn/HBC. What is more, MnO 2 and CuO (or Cu 2 O) were highly dispersed on the CuMn/HBC surface. The strong synergistic effect between Cu-Mn mixed oxides was critical to the removal reaction of HCHO and Hg 0 via the redox equilibrium of Mn 4+ + Cu + ↔ Mn 3+ + Cu 2+ .

Adolescent cannabis use, change in neurocognitive function, and high-school graduation: A longitudinal study from early adolescence to young adulthood.

PubMed

Castellanos-Ryan, Natalie; Pingault, Jean-Baptiste; Parent, Sophie; Vitaro, Frank; Tremblay, Richard E; Séguin, Jean R

2017-10-01

The main objective of this prospective longitudinal study was to investigate bidirectional associations between adolescent cannabis use (CU) and neurocognitive performance in a community sample of 294 young men from ages 13 to 20 years. The results showed that in early adolescence, and prior to initiation to CU, poor short-term and working memory, but high verbal IQ, were associated with earlier age of onset of CU. In turn, age of CU onset and CU frequency across adolescence were associated with (a) specific neurocognitive decline in verbal IQ and executive function tasks tapping trial and error learning and reward processing by early adulthood and (b) lower rates of high-school graduation. The association between CU onset and change in neurocognitive function, however, was found to be accounted for by CU frequency. Whereas the link between CU frequency across adolescence and change in verbal IQ was explained (mediated) by high school graduation, the link between CU frequency and tasks tapping trial and error learning were independent from high school graduation, concurrent cannabis and other substance use, adolescent alcohol use, and externalizing behaviors. Findings support prevention efforts aimed at delaying onset and reducing frequency of CU.

Effects of the molecule-electrode interface on the low-bias conductance of Cu-H2-Cu single-molecule junctions.

PubMed

Jiang, Zhuoling; Wang, Hao; Shen, Ziyong; Sanvito, Stefano; Hou, Shimin

2016-07-28

The atomic structure and electronic transport properties of a single hydrogen molecule connected to both symmetric and asymmetric Cu electrodes are investigated by using the non-equilibrium Green's function formalism combined with the density functional theory. Our calculations show that in symmetric Cu-H2-Cu junctions, the low-bias conductance drops rapidly upon stretching, while asymmetric ones present a low-bias conductance spanning the 0.2-0.3 G0 interval for a wide range of electrode separations. This is in good agreement with experiments on Cu atomic contacts in a hydrogen environment. Furthermore, the distribution of the calculated vibrational energies of the two hydrogen atoms in the asymmetric Cu-H2-Cu junction is also consistent with experiments. These findings provide clear evidence for the formation of asymmetric Cu-H2-Cu molecular junctions in breaking Cu atomic contacts in the presence of hydrogen and are also helpful for the design of molecular devices with Cu electrodes.

Towards functionalization of graphene: in situ study of the nucleation of copper-phtalocyanine on graphene

NASA Astrophysics Data System (ADS)

Schwarz, Daniel; Henneke, Caroline; Kumpf, Christian

2016-02-01

Molecular films present an elegant way for the uniform functionalization or doping of graphene. Here, we present an in situ study on the initial growth of copper phthalocyanine (CuPc) on epitaxial graphene on Ir(111). We followed the growth up to a closed monolayer with low energy electron microscopy and selected area electron diffraction (μLEED). The molecules coexist on graphene in a disordered phase without long-range order and an ordered crystalline phase. The local topography of the graphene substrate plays an important role in the nucleation process of the crystalline phase. Graphene flakes on Ir(111) feature regions that are under more tensile stress than others. We observe that the CuPc molecules form ordered domains initially on those graphene regions that are closest to the fully relaxed lattice. We attribute this effect to a stronger influence of the underlying Ir(111) substrate for molecules adsorbed on those relaxed regions.

Study of Thermodynamics of Liquid Noble-Metals Alloys Through a Pseudopotential Theory

NASA Astrophysics Data System (ADS)

Vora, Aditya M.

2010-09-01

The Gibbs-Bogoliubov (GB) inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick (PY) hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F), and Sarkar et al. (S) is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function.

Sol-gel synthesis of fine Gd{sub 2}CuO{sub 4} particles: Influence of synthesis variables

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

Mahia, J.; Vazquez-Vazquez, C.; Basadre-Pampin, M.I.

1996-02-01

Fine particles of Gd{sub 2}CuO{sub 4} were prepared by a sol-gel reaction of an aqueous solution of metal nitrates in the presence of urea, which leads to high-homogeneity polycrystalline powders of Gd{sub 2}CuO{sub 4}. The authors have studied the synthesis conditions, demonstrating the existence of a relationship between the calcination temperature and the heating time needed to attain the pure phase. Gd{sub 2}CuO{sub 4} was obtained at temperatures of the order of 650 C, lower than temperatures employed in the conventional ceramic technique. The influence of the [urea]/[salts] ratio and an excess of Cu(II) in the starting solution was alsomore » studied and discussed. X-ray powder diffraction inductively coupled plasma atomic emission spectroscopy (ICPAES), photon correlation spectroscopy (PCS), and transmission electron microscopy (TEM) were used to characterize the Gd{sub 2}CuO{sub 4} samples obtained.« less

Influence of text type, topic familiarity, and stuttering frequency on listener recall, comprehension, and mental effort.

PubMed

Panico, James; Healey, E Charles

2009-04-01

To determine how text type, topic familiarity, and stuttering frequency influence listener recall, comprehension, and perceived mental effort. Sixty adults listened to familiar and unfamiliar narrative and expository texts produced with 0%, 5%, 10%, and 15% stuttering. Participants listened to 4 experimental text samples at only 1 stuttering frequency. After hearing the text samples, each listener performed a free recall task, answered cued recall questions, answered story comprehension questions, and rated their perceived mental effort. Free and cued recall as well as story comprehension scores were higher for narrative than for expository texts. Free and cued recall scores were better for familiar than for unfamiliar stories, although topic familiarity did not affect story comprehension scores. Samples with all levels of stuttering resulted in higher mental effort ratings for both text types and topic familiarities. Stuttering has a greater influence on listener recall and comprehension for narrative than for expository texts. Topic familiarity affects free and cued recall but has no influence on story comprehension. Regardless of the amount of stuttering, mental effort was high for both text types and levels of familiarity.

As(V) removal capacity of FeCu bimetallic nanoparticles in aqueous solutions: The influence of Cu content and morphologic changes in bimetallic nanoparticles.

PubMed

Sepúlveda, Pamela; Rubio, María A; Baltazar, Samuel E; Rojas-Nunez, J; Sánchez Llamazares, J L; Garcia, Alejandra García; Arancibia-Miranda, Nicolás

2018-08-15

In this study, bimetallic nanoparticles (BMNPs) with different mass ratios of Cu and Fe were evaluated. The influence of the morphology on the removal of pollutants was explored through theoretical and experimental studies, which revealed the best structure for removing arsenate (As(V)) in aqueous systems. To evidence the surface characteristics and differences among BMNPs with different mass proportions of Fe and Cu, several characterization techniques were used. Microscopy techniques and molecular dynamics simulations were applied to determine the differences in morphology and structure. In addition, X-ray diffraction (XRD) was used to determine the presence of various oxides. Finally, the magnetization response was evaluated, revealing differences among the materials. Our cumulative data show that BMNPs with low amounts of Cu (Fe 0.9 Cu 0.1 ) had a non-uniform core-shell structure with agglomerate-type chains of magnetite, whereas a Janus-like structure was observed in BMNPs with high amounts of Cu (Fe 0.5 Cu 0.5 ). However, a non-uniform core-shell structure (Fe 0.9 Cu 0.1 ) facilitated electron transfer among Fe, Cu and As, which increased the adsorption rate (k), capacity (q e ) and intensity (n). The mechanism of As removal was also explored in a comparative study of the phase and morphology of BMNPs pre- and post-sorption. Copyright © 2018 Elsevier Inc. All rights reserved.

Spatial part-set cuing facilitation.

PubMed

Kelley, Matthew R; Parasiuk, Yuri; Salgado-Benz, Jennifer; Crocco, Megan

2016-07-01

Cole, Reysen, and Kelley [2013. Part-set cuing facilitation for spatial information. Journal of Experimental Psychology: Learning, Memory, & Cognition, 39, 1615-1620] reported robust part-set cuing facilitation for spatial information using snap circuits (a colour-coded electronics kit designed for children to create rudimentary circuit boards). In contrast, Drinkwater, Dagnall, and Parker [2006. Effects of part-set cuing on experienced and novice chess players' reconstruction of a typical chess midgame position. Perceptual and Motor Skills, 102(3), 645-653] and Watkins, Schwartz, and Lane [1984. Does part-set cuing test for memory organization? Evidence from reconstructions of chess positions. Canadian Journal of Psychology/Revue Canadienne de Psychologie, 38(3), 498-503] showed no influence of part-set cuing for spatial information when using chess boards. One key difference between the two procedures was that the snap circuit stimuli were explicitly connected to one another, whereas chess pieces were not. Two experiments examined the effects of connection type (connected vs. unconnected) and cue type (cued vs. uncued) on memory for spatial information. Using chess boards (Experiment 1) and snap circuits (Experiment 2), part-set cuing facilitation only occurred when the stimuli were explicitly connected; there was no influence of cuing with unconnected stimuli. These results are potentially consistent with the retrieval strategy disruption hypothesis, as well as the two- and three-mechanism accounts of part-set cuing.

Elaboration, microstructure, propriétés électriques et magnétiques de matériaux textures dans les systèmes Nd-Ce-Cu-O et Bi-Sr-Ca-Cu-O

NASA Astrophysics Data System (ADS)

Dhalenne, G.; Trouilleux, L.; Jegoudez, J.; Revcolevschi, A.; Monod, P.; Kormann, R.; Ganne, J. P.; Motohira, N.; Kitazawa, K.

1991-11-01

Superconducting textured materials were grown from the melt by a floating zone technique in the Nd-Ce-Cu-O and Bi-Sr-Ca-Cu-O systems. The influence of growth conditions and starting compositions on the microstructures and phase composition of the samples were studied by optical microscopy under polarized light, electron microprobe analysis and X-ray diffraction. The superconducting properties of these samples were examined by both electrical resistivity and magnetic measurements. A very strong influence of the microstructure on the superconducting properties as well as a magnetic and electrical anisotropy were shown. In the case of the Bi-Sr-Ca-Cu-O system, critical current densities ranging from 1 600 to 3 000 A.cm^{-2} were measured at 77 K. Des matériaux supraconducteurs texturés ont été élaborés à partir de l'état liquide dans les systèmes Nd-Ce-Cu-O et Bi-Sr-Ca-Cu-O par une technique de fusion de zone. L'influence des conditions de croissance et des compositions initiales sur la microstructure des échantillons a été étudiée par microscopie optique en lumière polarisée, microsonde électronique et diffraction des rayons X. Les propriétés supraconductrices des échantillons ont été examinées par des mesures électriques et magnétiques. Il a été observé une forte influence de la microstructure sur les propriétés supraconductrices ainsi qu'une anisotropie électrique et magnétique. Dans le cas du système Bi-Sr-Ca-Cu-O, les densités de courant critique mesurées à 77 K sont comprises entre 1 600 et 3 000 A.cm^{-2}.

Junction formation of Cu3BiS3 investigated by Kelvin probe force microscopy and surface photovoltage measurements

PubMed Central

Mesa, Fredy; Chamorro, William; Vallejo, William; Baier, Robert; Dittrich, Thomas; Grimm, Alexander; Lux-Steiner, Martha C

2012-01-01

Summary Recently, the compound semiconductor Cu3BiS3 has been demonstrated to have a band gap of ~1.4 eV, well suited for photovoltaic energy harvesting. The preparation of polycrystalline thin films was successfully realized and now the junction formation to the n-type window needs to be developed. We present an investigation of the Cu3BiS3 absorber layer and the junction formation with CdS, ZnS and In2S3 buffer layers. Kelvin probe force microscopy shows the granular structure of the buffer layers with small grains of 20–100 nm, and a considerably smaller work-function distribution for In2S3 compared to that of CdS and ZnS. For In2S3 and CdS buffer layers the KPFM experiments indicate negatively charged Cu3BiS3 grain boundaries resulting from the deposition of the buffer layer. Macroscopic measurements of the surface photovoltage at variable excitation wavelength indicate the influence of defect states below the band gap on charge separation and a surface-defect passivation by the In2S3 buffer layer. Our findings indicate that Cu3BiS3 may become an interesting absorber material for thin-film solar cells; however, for photovoltaic application the band bending at the charge-selective contact has to be increased. PMID:22497001

Junction formation of Cu(3)BiS(3) investigated by Kelvin probe force microscopy and surface photovoltage measurements.

PubMed

Mesa, Fredy; Chamorro, William; Vallejo, William; Baier, Robert; Dittrich, Thomas; Grimm, Alexander; Lux-Steiner, Martha C; Sadewasser, Sascha

2012-01-01

Recently, the compound semiconductor Cu(3)BiS(3) has been demonstrated to have a band gap of ~1.4 eV, well suited for photovoltaic energy harvesting. The preparation of polycrystalline thin films was successfully realized and now the junction formation to the n-type window needs to be developed. We present an investigation of the Cu(3)BiS(3) absorber layer and the junction formation with CdS, ZnS and In(2)S(3) buffer layers. Kelvin probe force microscopy shows the granular structure of the buffer layers with small grains of 20-100 nm, and a considerably smaller work-function distribution for In(2)S(3) compared to that of CdS and ZnS. For In(2)S(3) and CdS buffer layers the KPFM experiments indicate negatively charged Cu(3)BiS(3) grain boundaries resulting from the deposition of the buffer layer. Macroscopic measurements of the surface photovoltage at variable excitation wavelength indicate the influence of defect states below the band gap on charge separation and a surface-defect passivation by the In(2)S(3) buffer layer. Our findings indicate that Cu(3)BiS(3) may become an interesting absorber material for thin-film solar cells; however, for photovoltaic application the band bending at the charge-selective contact has to be increased.

The influence of copper concentration and source on ileal microbiota.

PubMed

Pang, Y; Patterson, J A; Applegate, T J

2009-03-01

Copper is normally supplemented in poultry diets as a growth promotant and antimicrobial. However, there are conflicting reports about the growth benefits and little information about how Cu affects the microbiota in the intestinal tract of poultry. Therefore, in vitro and in vivo experiments were conducted with broilers to determine the effects of Cu source and supplementation on ileal microbiota. The influence of Cu on growth of lactobacilli and Escherichia coli in media inoculated with ileal contents was determined in the first study. When Cu sulfate pentahydrate was supplemented to the cultures, quadratic increases in lactobacilli to graded concentrations of Cu up to 125 mg/kg and quadratic decreases in E. coli up to 250 mg/kg of Cu were observed after 24 h of incubation at 37 degrees C. However, when tribasic Cu chloride (TBCC) was supplemented, neither linear nor quadratic responses to graded concentrations of dietary Cu were observed on number of lactobacilli or number of E. coli. The effects of Cu and Cu source on ileal microbiota and growth performance in broiler chickens were determined in the second study. Bird performance was not affected by Cu source or concentration. The bacterial culture enumeration results revealed that supplementation with 187.5 mg/kg of Cu from Cu sulfate pentahydrate and TBCC had no effect on number of ileal lactobacilli of birds. The denaturing gradient gel electrophoresis analyses of ileal microbial communities revealed that neither Cu supplementation nor source had effects on the number of bacterial species predominant in the ileal digesta or associated with the ileal mucosa. Supplementation with TBCC supplementation significantly increased the similarity coefficients of microbiota in the ileal mucosa compared with cross-products of all individuals. This suggests that TBCC may alter the intestinal microbiota, yet this shift had no effect on bird performance.

Functional connectivity between prefrontal and parietal cortex drives visuo-spatial attention shifts.

PubMed

Heinen, Klaartje; Feredoes, Eva; Ruff, Christian C; Driver, Jon

2017-05-01

It is well established that the frontal eye-fields (FEF) in the dorsal attention network (DAN) guide top-down selective attention. In addition, converging evidence implies a causal role for the FEF in attention shifting, which is also known to recruit the ventral attention network (VAN) and fronto-striatal regions. To investigate the causal influence of the FEF as (part of) a central hub between these networks, we applied thetaburst transcranial magnetic stimulation (TBS) off-line, combined with functional magnetic resonance (fMRI) during a cued visuo-spatial attention shifting paradigm. We found that TBS over the right FEF impaired performance on a visual discrimination task in both hemifields following attention shifts, while only left hemifield performance was affected when participants were cued to maintain the focus of attention. These effects recovered ca. 20min post stimulation. Furthermore, particularly following attention shifts, TBS suppressed the neural signal in bilateral FEF, right inferior and superior parietal lobule (IPL/SPL) and bilateral supramarginal gyri (SMG). Immediately post stimulation, functional connectivity was impaired between right FEF and right SMG as well as right putamen. Importantly, the extent of decreased connectivity between right FEF and right SMG correlated with behavioural impairment following attention shifts. The main finding of this study demonstrates that influences from right FEF on SMG in the ventral attention network causally underly attention shifts, presumably by enabling disengagement from the current focus of attention. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

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

PubMed

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

2017-05-01

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

Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines

NASA Astrophysics Data System (ADS)

Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.

2017-09-01

Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.

Effect of sonication on particle dispersion, administered dose and metal release of non-functionalized, non-inert metal nanoparticles.

PubMed

Pradhan, Sulena; Hedberg, Jonas; Blomberg, Eva; Wold, Susanna; Odnevall Wallinder, Inger

2016-01-01

In this study, we elucidate the effect of different sonication techniques to efficiently prepare particle dispersions from selected non-functionalized NPs (Cu, Al, Mn, ZnO), and corresponding consequences on the particle dose, surface charge and release of metals. Probe sonication was shown to be the preferred method for dispersing non-inert, non-functionalized metal NPs (Cu, Mn, Al). However, rapid sedimentation during sonication resulted in differences between the real and the administered doses in the order of 30-80 % when sonicating in 1 and 2.56 g/L NP stock solutions. After sonication, extensive agglomeration of the metal NPs resulted in rapid sedimentation of all particles. DLVO calculations supported these findings, showing the strong van der Waals forces of the metal NPs to result in significant NP agglomeration. Metal release from the metal NPs was slightly increased by increased sonication. The addition of a stabilizing agent (bovine serum albumin) had an accelerating effect on the release of metals in sonicated solutions. For Cu and Mn NPs, the extent of particle dissolution increased from <1.6 to ~5 % after sonication for 15 min. A prolonged sonication time (3-15 min) had negligible effects on the zeta potential of the studied NPs. In all, it is shown that it is of utmost importance to carefully investigate how sonication influences the physico-chemical properties of dispersed metal NPs. This should be considered in nanotoxicology investigations of metal NPs.

Using new hetero-spectral two-dimensional correlation analyses and synchrotron-radiation-based spectromicroscopy to characterize binding of Cu to soil dissolved organic matter.

PubMed

Sun, Fusheng; Li, Yaqing; Wang, Xiang; Chi, Zhilai; Yu, Guanghui

2017-04-01

Understanding the binding characteristics of copper (Cu) to different functional groups in soil dissolved organic matter (DOM) is important to explore Cu toxicity, bioavailability and ultimate fate in the environment. However, the methods used to explore such binding characteristics are still limited. Here, two-dimensional correlation spectroscopy (2DCOS) integrated with Fourier transform infrared (FTIR), 29 Si nuclear magnetic resonance (NMR), 27 Al NMR, and synchrotron-radiation-based FTIR spectromicroscopy were used to explore the binding characteristics of Cu to soil DOM as part of a long-term (23 years) fertilization experiment. Compared with no fertilization and inorganic fertilization (NPK), long-term pig manure fertilization (M) treatment significantly increased the concentration of total and bioavailable Cu in soils. Furthermore, hetero-spectral 2DCOS analyses demonstrated that the binding characteristics of Cu onto functional groups in soil DOM were modified by fertilization regimes. In the NPK treatment, Cu was bound to aliphatic C, whereas in the manure treatment SiO groups had higher affinity toward Cu than aliphatic C. Also, the sequence of binding of functional groups to Cu was modified by the fertilization treatments. Moreover, synchrotron-radiation-based FTIR spectromicroscopy showed that Cu, clay minerals and sesquioxides, and C functional groups were heterogeneously distributed at the micro-scale. Specifically, clay-OH as well as mineral elements had a distribution pattern similar to Cu, but certain (but not all) C forms showed a distribution pattern inconsistent with that of Cu. The combination of synchrotron radiation spectromicroscopy and 2DCOS is a useful tool in exploring the interactions among heavy metals, minerals and organic components in soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modular "Click" Preparation of Bifunctional Polymeric Heterometallic Catalysts.

PubMed

Wang, Wenlong; Zhao, Liyuan; Lv, Hui; Zhang, Guodong; Xia, Chungu; Hahn, F Ekkehardt; Li, Fuwei

2016-06-27

Heterobimetallic molecular complexes or strictly alternating metallated polymers are obtained by a click reaction between mononuclear metal complexes (secondary building units, SBUs) bearing NHCs functionalized with either p-azidophenyl or p-ethynylphenyl wingtips. With a copper-NHC complex as SBU the formation of molecular or polymeric compounds did not require any additives as the copper complex catalyzes the click reaction. Transmetallation from heterobimetallic Cu/Ag derivatives to Cu/Pd derivatives was achieved. The linker between the SBUs (flexible or rigid) influences the catalytic activity of the heterobimetallic compounds. The polymer with alternating copper-NHC and silver-NHC units and a flexible methylene-triazole bridge between them shows the highest activity in the catalytic alkynylation of trifluoromethyl ketones to give fluorinated propargylic alcohols. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailoring the structure of metal oxide nanostructures towards enhanced sensing properties for environmental applications.

PubMed

Yang, Mingqing; He, Junhui

2012-02-15

The present article reviews recent works in our laboratory about the sensing properties to toxic gases using nanostructured WO(3), TiO(2), FTiO(2), and CuO functionalized quartz crystal microbalance (QCM) sensors. WO(3) and TiO(2) functionalized QCM sensors have much shorter response time than those functionalized by conventional hydrogen-bond acidic branched copolymers for detection of dimethyl methylphosphonate (DMMP). FTiO(2) functionalized QCM sensors can improve the gas sensing characteristics by shortening the response time but at the price of partial irreversibility. The sensing mechanism was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Varied CuO nanostructures were synthesized by simple modulation of reaction conditions. All the as-prepared CuO was applied on QCM resonators and explored for HCN sensing. Surprisingly, responses of all the sensors to HCN were found to be in an opposite direction as compared with other common volatile substances, offering excellent selectivity for HCN detection. The sensitivity was very high, and the response and recovery were very fast. Comparison of the specific surface areas of CuO nanostructures showed that CuO of higher surface area is more sensitive than that of lower surface area, indicating that the specific surface area of these CuO nanostructures plays an important role in the sensitivity of related sensors. Based on experimental results, a sensing mechanism was proposed in which a surface redox reaction occurs between CuO and Cu(2)O on the CuO nanostructures reversibly upon contact with HCN and air, respectively. The CuO functionalized QCM sensors are considered to be a promising candidate for trace HCN gas detection in practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Copper interstitial recombination centers in Cu 3 N

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

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam

We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

Copper interstitial recombination centers in Cu 3 N

DOE PAGES

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; ...

2018-06-04

We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

Intrinsically Radioactive [64Cu]CuInS/ZnS Quantum Dots for PET and Optical Imaging: Improved Radiochemical Stability and Controllable Cerenkov Luminescence

PubMed Central

2015-01-01

Functionalized quantum dots (QDs) have been widely explored for multimodality bioimaging and proven to be versatile agents. Attaching positron-emitting radioisotopes onto QDs not only endows their positron emission tomography (PET) functionality, but also results in self-illuminating QDs, with no need for an external light source, by Cerenkov resonance energy transfer (CRET). Traditional chelation methods have been used to incorporate the radionuclide, but these methods are compromised by the potential for loss of radionuclide due to cleavage of the linker between particle and chelator, decomplexation of the metal, and possible altered pharmacokinetics of nanomaterials. Herein, we described a straightforward synthesis of intrinsically radioactive [64Cu]CuInS/ZnS QDs by directly incorporating 64Cu into CuInS/ZnS nanostructure with 64CuCl2 as synthesis precursor. The [64Cu]CuInS/ZnS QDs demonstrated excellent radiochemical stability with less than 3% free 64Cu detected even after exposure to serum containing EDTA (5 mM) for 24 h. PEGylation can be achieved in situ during synthesis, and the PEGylated radioactive QDs showed high tumor uptake (10.8% ID/g) in a U87MG mouse xenograft model. CRET efficiency was studied as a function of concentration and 64Cu radioactivity concentration. These [64Cu]CuInS/ZnS QDs were successfully applied as an efficient PET/self-illuminating luminescence in vivo imaging agents. PMID:25549258

Intrinsically radioactive [64Cu]CuInS/ZnS quantum dots for PET and optical imaging: improved radiochemical stability and controllable Cerenkov luminescence.

PubMed

Guo, Weisheng; Sun, Xiaolian; Jacobson, Orit; Yan, Xuefeng; Min, Kyunghyun; Srivatsan, Avinash; Niu, Gang; Kiesewetter, Dale O; Chang, Jin; Chen, Xiaoyuan

2015-01-27

Functionalized quantum dots (QDs) have been widely explored for multimodality bioimaging and proven to be versatile agents. Attaching positron-emitting radioisotopes onto QDs not only endows their positron emission tomography (PET) functionality, but also results in self-illuminating QDs, with no need for an external light source, by Cerenkov resonance energy transfer (CRET). Traditional chelation methods have been used to incorporate the radionuclide, but these methods are compromised by the potential for loss of radionuclide due to cleavage of the linker between particle and chelator, decomplexation of the metal, and possible altered pharmacokinetics of nanomaterials. Herein, we described a straightforward synthesis of intrinsically radioactive [(64)Cu]CuInS/ZnS QDs by directly incorporating (64)Cu into CuInS/ZnS nanostructure with (64)CuCl2 as synthesis precursor. The [(64)Cu]CuInS/ZnS QDs demonstrated excellent radiochemical stability with less than 3% free (64)Cu detected even after exposure to serum containing EDTA (5 mM) for 24 h. PEGylation can be achieved in situ during synthesis, and the PEGylated radioactive QDs showed high tumor uptake (10.8% ID/g) in a U87MG mouse xenograft model. CRET efficiency was studied as a function of concentration and (64)Cu radioactivity concentration. These [(64)Cu]CuInS/ZnS QDs were successfully applied as an efficient PET/self-illuminating luminescence in vivo imaging agents.

Effect of cultivation ages on Cu accumulation in Greenhouse Soils in North China

NASA Astrophysics Data System (ADS)

Wang, Jun; Guo, Wenmiao; Chen, Xin; Shi, Yi

2017-11-01

In this study, we determined the influence of cultivation age on Cu accumulation in greenhouse soils. The concentration of plant available Cu (A-Cu) decreased with depth, and the contents of top soils (0-40 cm) in greenhouses were higher than those of the open field. There was a positive correlation between A-Cu concentrations in soils and cultivation ages (R2=0.572). The contents of total Cu (T-Cu) decreased with depth, and positively correlated with cultivation ages in top soils (0-20cm) (R2=0.446). The long-term usage of manures can cause Cu increase and accumulation in greenhouse soils in comparison to the open field.

Controlled fabrication of photoactive copper oxide-cobalt oxide nanowire heterostructures for efficient phenol photodegradation.

PubMed

Shi, Wenwu; Chopra, Nitin

2012-10-24

Fabrication of oxide nanowire heterostructures with controlled morphology, interface, and phase purity is critical for high-efficiency and low-cost photocatalysis. Here, we have studied the formation of copper oxide-cobalt nanowire heterostructures by sputtering and subsequent air annealing to result in cobalt oxide (Co(3)O(4))-coated CuO nanowires. This approach allowed fabrication of standing nanowire heterostructures with tunable compositions and morphologies. The vertically standing CuO nanowires were synthesized in a thermal growth method. The shell growth kinetics of Co and Co(3)O(4) on CuO nanowires, morphological evolution of the shell, and nanowire self-shadowing effects were found to be strongly dependent on sputtering duration, air-annealing conditions, and alignment of CuO nanowires. Finite element method (FEM) analysis indicated that alignment and stiffness of CuO-Co nanowire heterostructures greatly influenced the nanomechanical aspects such as von Mises equivalent stress distribution and bending of nanowire heterostructures during the Co deposition process. This fundamental knowledge was critical for the morphological control of Co and Co(3)O(4) on CuO nanowires with desired interfaces and a uniform coating. Band gap energies and phenol photodegradation capability of CuO-Co(3)O(4) nanowire heterostructures were studied as a function of Co(3)O(4) morphology. Multiple absorption edges and band gap tailings were observed for these heterostructures, indicating photoactivity from visible to UV range. A polycrystalline Co(3)O(4) shell on CuO nanowires showed the best photodegradation performance (efficiency ~50-90%) in a low-powered UV or visible light illumination with a sacrificial agent (H(2)O(2)). An anomalously high efficiency (~67.5%) observed under visible light without sacrificial agent for CuO nanowires coated with thin (∼5.6 nm) Co(3)O(4) shell and nanoparticles was especially interesting. Such photoactive heterostructures demonstrate unique sacrificial agent-free, robust, and efficient photocatalysts promising for organic decontamination and environmental remediation.

Influence of Oxygen on Cu Distribution Behavior Between Molten Iron and FeS-Based Flux

NASA Astrophysics Data System (ADS)

Kang, Youngjo; Shin, Kil-Sun; Morita, Kazuki

2018-06-01

Cu distribution behavior between molten iron and a sulfide flux was investigated under different oxygen contents in the sulfide flux to clarify the effect of oxygen content in FeS-based flux on Cu removal. The activity coefficient of CuS0.5 could be experimentally estimated according to the oxygen content. Based on the present result, the possibility of Cu removal by sulfide flux containing a certain amount of oxide was discussed.

Interactions between callous unemotional behaviors and executive function in early childhood predict later socioemotional functioning

PubMed Central

Waller, Rebecca; Hyde, Luke W.; Baskin-Sommers, Arielle; Olson, Sheryl L.

2018-01-01

Callous unemotional (CU) behaviors are linked to aggression, behavior problems, and difficulties in peer relationships in children and adolescents. However, few studies have examined whether early childhood CU behaviors predict aggression or peer-rejection during late-childhood or potential moderation of this relationship by executive function. The current study examined whether the interaction of CU behaviors and executive function in early childhood predicted different forms of aggression in late-childhood, including proactive, reactive, and relational aggression, as well as how much children were liked by their peers. Data from cross-informant reports and multiple observational tasks were collected from a high-risk sample (N=240; female=118) at ages 3 and 10 years old. Parent reports of CU behaviors at age 3 predicted teacher reports of reactive, proactive, and relational aggression, as well as lower peer-liking at age 10. Moderation analysis showed that specifically at high levels of CU behaviors and low levels of observed executive function, children were reported by teachers as showing greater reactive and proactive aggression, and were less-liked by peers. Findings demonstrate that early childhood CU behaviors and executive function have unique main and interactive effects on both later aggression and lower peer-liking even when taking into account stability in behavior problems over time. By elucidating how CU behaviors and deficits in executive function potentiate each other during early childhood, we can better characterize the emergence of severe and persistent behavior and interpersonal difficulties across development. PMID:27418255

Effects of copper, hypoxia and acute temperature shifts on mitochondrial oxidation in rainbow trout (Oncorhynchus mykiss) acclimated to warm temperature.

PubMed

Sappal, Ravinder; Fast, Mark; Stevens, Don; Kibenge, Fred; Siah, Ahmed; Kamunde, Collins

2015-12-01

Temperature fluctuations, hypoxia and metals pollution frequently occur simultaneously or sequentially in aquatic systems and their interactions may confound interpretation of their biological impacts. With a focus on energy homeostasis, the present study examined how warm acclimation influences the responses and interactions of acute temperature shift, hypoxia and copper (Cu) exposure in fish. Rainbow trout (Oncorhynchus mykiss) were acclimated to cold (11°C; control) and warm (20°C) temperature for 3 weeks followed by exposure to environmentally realistic levels of Cu and hypoxia for 24h. Subsequently, mitochondrial electron transport system (ETS) respiratory activity supported by complexes I-IV (CI-IV), plasma metabolites and condition indices were measured. Warm acclimation reduced fish condition, induced aerobic metabolism and altered the responses of fish to acute temperature shift, hypoxia and Cu. Whereas warm acclimation decelerated the ETS and increased the sensitivity of maximal oxidation rates of the proximal (CI and II) complexes to acute temperature shift, it reduced the thermal sensitivity of state 4 (proton leak). Effects of Cu with and without hypoxia were variable depending on the acclimation status and functional index. Notably, Cu stimulated respiratory activity in the proximal ETS segments, while hypoxia was mostly inhibitory and minimized the stimulatory effect of Cu. The effects of Cu and hypoxia were modified by temperature and showed reciprocal antagonistic interaction on the ETS and plasma metabolites, with modest additive actions limited to CII and IV state 4. Overall, our results indicate that warm acclimation came at a cost of reduced ETS efficiency and increased sensitivity to added stressors. Copyright © 2015 Elsevier B.V. All rights reserved.

Coordination properties of the oxime analogue of glycine to Cu(II).

PubMed

Georgieva, I; Trendafilova, N; Rodríguez-Santiago, L; Sodupe, M

2005-06-30

The coordination of Cu2+ by glyoxilic acid oxime (gao)--the oxime analogue of glycine amino acid--and its deprotonated (gao- and gao2-) species has been studied with different density functional methods. Single-point calculations have also been carried out at the single- and double- (triple) excitation coupled-cluster (CCSD(T)) level of theory. The isomers studied involve coordination of Cu2+ to electron-rich sites (O,N) of neutral, anionic, and dianionic gao species in different conformations. In contrast to Cu2+-glycine, for which the ground-state structure is bidentate with the CO2(-) terminus of zwitterionic glycine, for Cu2+-gao the most stable isomer shows monodentate binding of Cu2+ with the carbonylic oxygen of the neutral form. The most stable complexes of Cu2+ interacting with deprotonated gao species (gao- and gao2-) also take place through the carboxylic oxygens but in a bidentate manner. The results with different functionals show that, for these open shell (Cu2+-L) systems, the relative stability of complexes with different coordination environments (and so, different spin distribution) can be quite sensitive to the amount of "Hartree-Fock" exchange included in the functional. Among all the functionals tested in this work, the BHandHLYP is the one that better compares to CCSD(T) results.

Controlling Surface Termination and Facet Orientation in Cu2O Nanoparticles for High Photocatalytic Activity: A Combined Experimental and Density Functional Theory Study.

PubMed

Su, Yang; Li, Hongfei; Ma, Hanbin; Robertson, John; Nathan, Arokia

2017-03-08

Cu 2 O nanoparticles with controllable facets are of great significance for photocatalysis. In this work, the surface termination and facet orientation of Cu 2 O nanoparticles are accurately tuned by adjusting the amount of hydroxylamine hydrochloride and surfactant. It is found that Cu 2 O nanoparticles with Cu-terminated (110) or (111) surfaces show high photocatalytic activity, while other exposed facets show poor reactivity. Density functional theory simulations confirm that sodium dodecyl sulfate surfactant can lower the surface free energy of Cu-terminated surfaces, increase the density of exposed Cu atoms at the surfaces and thus benefit the photocatalytic activity. It also shows that the poor reactivity of the Cu-terminated Cu 2 O (100) surface is due to the high energy barrier of holes at the surface region.

In situ codoping of a CuO absorber layer with aluminum and titanium: the impact of codoping and interface engineering on the performance of a CuO-based heterojunction solar cell

NASA Astrophysics Data System (ADS)

Masudy-Panah, Saeid; Radhakrishnan, K.; Ru, Tan Hui; Yi, Ren; Wong, Ten It; Dalapati, Goutam Kumar

2016-09-01

Aluminum-doped cupric oxide (CuO:Al) was prepared via an out-diffusion process of Al from an Al-coated substrate into the deposited CuO thin film upon thermal treatment. The effect of the annealing temperature on the structural and optical properties of CuO:Al was investigated in detail. The influence of Al incorporation on the photovoltaic properties was then investigated by preparing a p-CuO:Al/n-Si heterojunction solar cell. A significant improvement in the performance of the solar cell was achieved by controlling the out-diffusion of Al. A novel in situ method to co-dope CuO with Al and titanium (Ti) has been proposed to demonstrate CuO-based solar cells with the front surface field (FSF) design. The FSF design was created by depositing a CuO:Al layer followed by a Ti-doped CuO (CuO:Ti) layer. This is the first successful experimental demonstration of the codoping of a CuO thin film and CuO thin film solar cells with the FSF design. The open circuit voltage (V oc), short circuit current density (J sc) and fill factor (FF) of the fabricated solar cells were significantly higher for the FSF device compared to devices without FSF. The FF of this device improved by 68% through the FSF design and a record efficiency ɳ of 2% was achieved. The improvement of the solar cell properties is mainly attributed to the reduction of surface recombination, which influences the charge carrier collection.

Adolescent cannabis use, change in neurocognitive function, and high-school graduation: A longitudinal study from early adolescence to young adulthood

PubMed Central

CASTELLANOS-RYAN, NATALIE; PINGAULT, JEAN-BAPTISTE; PARENT, SOPHIE; VITARO, FRANK; TREMBLAY, RICHARD E.; SÉGUIN, JEAN R.

2017-01-01

The main objective of this prospective longitudinal study was to investigate bidirectional associations between adolescent cannabis use (CU) and neurocognitive performance in a community sample of 294 young men from ages 13 to 20 years. The results showed that in early adolescence, and prior to initiation to CU, poor short-term and working memory, but high verbal IQ, were associated with earlier age of onset of CU. In turn, age of CU onset and CU frequency across adolescence were associated with (a) specific neurocognitive decline in verbal IQ and executive function tasks tapping trial and error learning and reward processing by early adulthood and (b) lower rates of high-school graduation. The association between CU onset and change in neurocognitive function, however, was found to be accounted for by CU frequency. Whereas the link between CU frequency across adolescence and change in verbal IQ was explained (mediated) by high school graduation, the link between CU frequency and tasks tapping trial and error learning were independent from high school graduation, concurrent cannabis and other substance use, adolescent alcohol use, and externalizing behaviors. Findings support prevention efforts aimed at delaying onset and reducing frequency of CU. PMID:28031069

As(III) Removal from Drinking Water by Carbon Nanotube Membranes with Magnetron-Sputtered Copper: Performance and Mechanisms.

PubMed

Luan, Hongyan; Zhang, Quan; Cheng, Guo-An; Huang, Haiou

2018-06-20

Current approaches for functionalizing carbon nanotubes (CNTs) often utilize harsh chemical conditions, and the resulting harmful wastes can cause various environmental and health concerns. In this study, magnetron sputtering technique is facilely employed to functionalize CNT membranes by depositing Cu onto premade CNT membranes without using any chemical treatment. A comparative evaluation of the substrate polymeric membrane (mixed cellulose ester (MCE)), MCE sputtered with copper (Cu/MCE), the pristine CNT membrane (CNT), and CNT membrane sputtered with Cu (Cu/CNT) shows that Cu/CNT possesses mechanically stable structures and similar membrane permeability as MCE. More importantly, Cu/CNT outperforms other membranes with high As(III) removal efficiency of above 90%, as compared to less than 10% by MCE and CNT, and 75% by Cu/MCE from water. The performance of Cu/CNT membranes for As(III) removal is also investigated as a function of ionic strength, sputtering time, co-existing ions, solution pH, and the reusability. Further characterizations of As speciation in the filtrate and on Cu/CNT reveal that arsenite removal by Cu/CNT possibly began with Cu-catalyzed oxidation of arsenite to arsenate, followed by adsorptive filtration of arsenate by the membrane. Overall, this study demonstrates that magnetron sputtering is a promising greener technology for the productions of metal-CNT composite membranes for environmental applications.

Chemical and structural characterization of copper adsorbed on mosses (Bryophyta).

PubMed

González, Aridane G; Jimenez-Villacorta, Felix; Beike, Anna K; Reski, Ralf; Adamo, Paola; Pokrovsky, Oleg S

2016-05-05

The adsorption of copper on passive biomonitors (devitalized mosses Hypnum sp., Sphagnum denticulatum, Pseudoscleropodium purum and Brachythecium rutabulum) was studied under different experimental conditions such as a function of pH and Cu concentration in solution. Cu assimilation by living Physcomitrella patents was also investigated. Molecular structure of surface adsorbed and incorporated Cu was studied by X-ray Absorption Spectroscopy (XAS). Devitalized mosses exhibited the universal adsorption pattern of Cu as a function of pH, with a total binding sites number 0.05-0.06 mmolg(dry)(-1) and a maximal adsorption capacity of 0.93-1.25 mmolg(dry)(-1) for these devitalized species. The Extended X-ray Absorption Fine Structure (EXAFS) fit of the first neighbor demonstrated that for all studied mosses there are ∼4.5 O/N atoms around Cu at ∼1.95 Å likely in a pseudo-square geometry. The X-ray Absorption Near Edge Structure (XANES) analysis demonstrated that Cu(II)-cellulose (representing carboxylate groups) and Cu(II)-phosphate are the main moss surface binding moieties, and the percentage of these sites varies as a function of solution pH. P. patens exposed during one month to Cu(2+) yielded ∼20% of Cu(I) in the form of Cu-S(CN) complexes, suggesting metabolically-controlled reduction of adsorbed and assimilated Cu(2+). Copyright © 2016 Elsevier B.V. All rights reserved.

Density-functional theory study of dimethyl carbonate synthesis by methanol oxidative carbonylation on single-atom Cu1/graphene catalyst

NASA Astrophysics Data System (ADS)

Sun, Wei; Shi, Ruina; Wang, Xuhui; Liu, Shusen; Han, Xiaoxia; Zhao, Chaofan; Li, Zhong; Ren, Jun

2017-12-01

The mechanism for dimethyl carbonate (DMC) synthesis by oxidation carbonylation of methanol on a single-atom Cu1/graphene catalyst was investigated by density-functional theory calculations. Carbon vacancies in graphene can significantly enhance the interaction between Cu atoms and graphene supports, and provide an increased transfer of electrons from Cu atoms to the graphene sheet. Compared with Cu-doped divacancy graphene (Cu/DG), Cu-doped monovacancy graphene (Cu/MG) provides a stronger interaction between adsorbents and the catalyst surface. Among the reaction processes over Cu1/graphene catalysts, CO insertion into methoxide was more favorable than dimethoxide. The rate-limiting step on the Cu/DG surface is the carbomethoxide reaction with methoxide, which is exothermic by 164.6 kJ mol-1 and has an activation barrier of 190.9 kJ mol-1 energy. Compared with that on the Cu crystal surface, Cu4 and Cu3Rh clusters, and the Cu2O(111) surface, the rate-determining step for DMC formation on Cu/MG, which is CO insertion into methoxide, needs to overcome the lowest barrier of 73.5 kJ mol-1 and is exothermic by 44.6 kJ mol-1. Therefore, Cu/MG was beneficial to the formation of DMC as a single-atom catalyst.

Effect of magnetic ion Ni doping for Cu in the CuO 2 plane on electronic structure and superconductivity on Y123 cuprate

NASA Astrophysics Data System (ADS)

Cao, Shixun; Li, Pinglin; Cao, Guixin; Zhang, Jincang

2003-05-01

The YBa2Cu3-xNixO7-δ with x=0-0.4 have been studied using positron annihilation technique. The changes of positron annihilation parameters with the Ni substitution concentration x are given. From the change of electronic density ne and Tc, it would prove that the localized carriers (electron and hole) in Cu-O chain and CuO2 planes have enormous influence on superconductivity by affecting charge transfer between the reservoir layer and CuO2 planes.

Effect of dopants on the TL response of the new LiF:Mg,Cu,Ag material

NASA Astrophysics Data System (ADS)

Yahyaabadi, A.; Torkzadeh, F.; Rezaei-Ochbelagh, D.; Hosseini Pooya, M.

2018-07-01

The new TL LiF:Mg,Cu,Ag material was prepared and investigated in this study. The TL intensity of LiF:Mg,Cu,Ag is strongly dependent on the concentration of dopants and the preparation procedure. Any small change in these factors can cause alterations in TL response. In this study, the influence of Cu and Ag concentrations on the response of the LiF:Mg,Cu,Ag sample was investigated and showed that the height of the low, main and high temperature peaks changes with Ag concentration. Their intensities increased with increasing Ag concentration to a maximum value and decreased with higher Ag concentration. It was also found that Cu concentration less than 0.05 mol% influences the maximum peak height and TL intensity. The optimum Cu and Ag concentrations were found to be 0.05 and 0.1 mol% at 1005 °C QT, respectively. The role of dopants in LiF:Mg,Cu,Ag material was also investigated. The results showed that presence of three dopants is important for having material with sensitivity higher than LiF:Mg,Ti. The Mg dopant plays a crucial role in the formation of the trapping center and the position of the main dosimetric peak.

Effects of Ag addition on solid–state interfacial reactions between Sn–Ag–Cu solder and Cu substrate

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

Yang, Ming

Low–Ag–content Sn–Ag–Cu (SAC) solders have attracted much recent attention in electronic packaging for their low cost. To reasonably reduce the Ag content in Pb–free solders, a deep understanding of the basic influence of Ag on the SAC solder/Cu substrate interfacial reaction is essential. Previous studies have discussed the influence of Ag on the interfacial intermetallic compound (IMC) thickness. However, because IMC growth is the joint result of multiple factors, such characterizations do not reveal the actual role of Ag. In this study, changes in interfacial IMCs after Ag introduction were systemically and quantitatively characterized in terms of coarsening behaviors, orientationmore » evolution, and growth kinetics. The results show that Ag in the solder alloy affects the coarsening behavior, accelerates the orientation concentration, and inhibits the growth of interfacial IMCs during solid–state aging. The inhibition mechanism was quantitatively discussed considering the individual diffusion behaviors of Cu and Sn atoms, revealing that Ag inhibits interfacial IMC growth primarily by slowing the diffusion of Cu atoms through the interface. - Highlights: •Role of Ag in IMC formation during Sn–Ag–Cu soldering was investigated. •Ag affects coarsening, crystallographic orientation, and IMC growth. •Diffusion pathways of Sn and Cu are affected differently by Ag. •Ag slows Cu diffusion to inhibit IMC growth at solder/substrate interface.« less

Inorganic anion-dependent assembly of zero-, one-, two- and three-dimensional Cu(II)/Ag(I) complexes under the guidance of the HSAB theory: Synthesis, structure, and magnetic property

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

Liu, Yaru; Xing, Zhiyan; Zhang, Xiao

To systematically explore the influence of inorganic anions on building coordination complexes, five novel complexes based on 1-(benzotriazole-1-methyl)−2-propylimidazole (bpmi), [Cu(bpmi){sub 2}(Ac){sub 2}]·H{sub 2}O (1), [Cu(bpmi){sub 2}(H{sub 2}O){sub 2}]·2NO{sub 3}·2H{sub 2}O (2), [Cu(bpmi)(N{sub 3}){sub 2}] (3), [Ag(bpmi)(NO{sub 3})] (4) and [Cu{sub 3}(bpmi){sub 2}(SCN){sub 4}(DMF)] (5) (Ac{sup −}=CH{sub 3}COO{sup −}, DMF=N,N-Dimethylformamide) are synthesized through rationally introducing Cu(II) salts and Ag(I) salt with different inorganic anions. X-ray single-crystal analyses reveal that these complexes show interesting structural features from mononuclear (1), one-dimensional (2 and 3), two-dimensional (4) to three-dimensional (5) under the influence of inorganic anions with different basicities. The structural variation can bemore » explained by the hard-soft-acid-base (HSAB) theory. Magnetic susceptibility measurement indicates that complex 3 exhibits an antiferromagnetic coupling between adjacent Cu(II) ions. - Graphical abstract: Five new Cu(II)/Ag(I) complexes show interesting structural features from mononuclear, one-dimension, two-dimension to three-dimension under the influence of inorganic anions. The structural variation can be explained by the HSAB theory. - Highlights: • Five inorganic anion-dependent complexes are synthesized. • Structural variation can be explained by the hard-soft-acid-base (HSAB) theory. • The magnetic property of complex has been studied.« less

Medications influencing central cholinergic pathways affect fixation stability, saccadic response time and associated eye movement dynamics during a temporally-cued visual reaction time task.

PubMed

Naicker, Preshanta; Anoopkumar-Dukie, Shailendra; Grant, Gary D; Modenese, Luca; Kavanagh, Justin J

2017-02-01

Anticholinergic medications largely exert their effects due to actions on the muscarinic receptor, which mediates the functions of acetylcholine in the peripheral and central nervous systems. In the central nervous system, acetylcholine plays an important role in the modulation of movement. This study investigated the effects of over-the-counter medications with varying degrees of central anticholinergic properties on fixation stability, saccadic response time and the dynamics associated with this eye movement during a temporally-cued visual reaction time task, in order to establish the significance of central cholinergic pathways in influencing eye movements during reaction time tasks. Twenty-two participants were recruited into the placebo-controlled, human double-blind, four-way crossover investigation. Eye tracking technology recorded eye movements while participants reacted to visual stimuli following temporally informative and uninformative cues. The task was performed pre-ingestion as well as 0.5 and 2 h post-ingestion of promethazine hydrochloride (strong centrally acting anticholinergic), hyoscine hydrobromide (moderate centrally acting anticholinergic), hyoscine butylbromide (anticholinergic devoid of central properties) and a placebo. Promethazine decreased fixation stability during the reaction time task. In addition, promethazine was the only drug to increase saccadic response time during temporally informative and uninformative cued trials, whereby effects on response time were more pronounced following temporally informative cues. Promethazine also decreased saccadic amplitude and increased saccadic duration during the temporally-cued reaction time task. Collectively, the results of the study highlight the significant role that central cholinergic pathways play in the control of eye movements during tasks that involve stimulus identification and motor responses following temporal cues.

Photocatalytic properties and selective antimicrobial activity of TiO2(Eu)/CuO nanocomposite

NASA Astrophysics Data System (ADS)

Michal, Robert; Dworniczek, Ewa; Caplovicova, Maria; Monfort, Olivier; Lianos, Panagiotis; Caplovic, Lubomir; Plesch, Gustav

2016-05-01

TiO2(Eu)/CuO nanocomposites were prepared by precipitation method. The anatase nanocrystallites with a size of 26 nm exhibited well crystallized and characteristical dipyramidal morphology and {1 0 1} and {0 0 1} faceting. Transmission electron microscopy photographs with atomic resolution showed that the Eu(III) dopants were bounded on surface of titania. In the composites, the CuO nanocrystals exhibiting a monoclinic tenorite structure with a size in the range from 2 to 5 nm were grafted to the surface of titania. The influence of copper(II) oxide led to distinct selectivity in the photocatalytic and antimicrobial properties of the investigated TiO2(Eu)/CuO nanocomposites. While the presence of CuO nanocrystals strongly increased the photocatalytic production of hydrogen by ethanol reforming, it decreased the activity in photoinduced total mineralization of phenol comparing with non-modified TiO2(Eu). In investigated TiO2(Eu)/CuO powders, the photoinduced antimicrobial activity against membranes of Enterococcus species was influenced by the selective binding of CuO to the surface of the microorganism leading to distinct selectivity in their action. The activity against Enterococcus faecalis was higher than against Enterococcus faecium.

Episodic feeling-of-knowing accuracy and cued recall in the elderly: evidence for double dissociation involving executive functioning and processing speed.

PubMed

Perrotin, Audrey; Isingrini, Michel; Souchay, Céline; Clarys, David; Taconnat, Laurence

2006-05-01

This research investigated adult age differences in a metamemory monitoring task-episodic feeling-of-knowing (FOK) and in an episodic memory task-cued recall. Executive functioning and processing speed were examined as mediators of these age differences. Young and elderly adults were administered an episodic FOK task, a cued recall task, executive tests and speed tests. Age-related decline was observed on all the measures. Correlation analyses revealed a pattern of double dissociation which indicates a specific relationship between executive score and FOK accuracy, and between speed score and cued recall. When executive functioning and processing speed were evaluated concurrently on FOK and cued recall variables, hierarchical regression analyses showed that executive score was a better mediator of age-related variance in FOK, and that speed score was the better mediator of age-related variance in cued recall.

Callous-Unemotional Traits and Autonomic Functioning in Toddlerhood Interact to Predict Externalizing Behaviors in Preschool.

PubMed

Wagner, Nicholas J; Hastings, Paul D; Rubin, Kenneth H

2017-11-29

Callous-unemotional (CU) traits are one meaningful risk factor which helps to explain heterogeneity in the emergence of externalizing behavior problems. While the extant literature demonstrates links between early CU traits and later externalizing problems, there is a dearth of research examining for whom early CU traits confer risk. Data from a longitudinal study (n = 108) were used to examine the extent to which parasympathetic functioning moderated links between CU traits in toddlerhood (m age  = 24.99 months) and externalizing behavior problems at preschool-age (m age  = 51 months). Neither CU traits nor parasympathetic functioning at age 2 directly predicted later externalizing behaviors. However, results show that high levels of CU traits predict elevated externalizing behavior problems, but only for toddlers exhibiting either high baseline respiratory sinus arrhythmia (RSA) or little to no RSA suppression in response to a fear stimulus.

Preparation of Advanced CuO Nanowires/Functionalized Graphene Composite Anode Material for Lithium Ion Batteries.

PubMed

Zhang, Jin; Wang, Beibei; Zhou, Jiachen; Xia, Ruoyu; Chu, Yingli; Huang, Jia

2017-01-17

The copper oxide (CuO) nanowires/functionalized graphene (f-graphene) composite material was successfully composed by a one-pot synthesis method. The f-graphene synthesized through the Birch reduction chemistry method was modified with functional group "-(CH₂)₅COOH", and the CuO nanowires (NWs) were well dispersed in the f-graphene sheets. When used as anode materials in lithium-ion batteries, the composite exhibited good cyclic stability and decent specific capacity of 677 mA·h·g -1 after 50 cycles. CuO NWs can enhance the lithium-ion storage of the composites while the f-graphene effectively resists the volume expansion of the CuO NWs during the galvanostatic charge/discharge cyclic process, and provide a conductive paths for charge transportation. The good electrochemical performance of the synthesized CuO/f-graphene composite suggests great potential of the composite materials for lithium-ion batteries anodes.

The effect dietary Cu intake on the development of hypertension in the Dahl-S rat

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

Garrow, T.; Metzler, G.; Clegg, M.S.

It has been shown that hypertense Dahl-S rats are characterized by abnormal Cu metabolism. To test the idea that variable dietary Cu intake may influence the development of hypertension in these rats, Dahl salt-sensitive rats were fed ad libitum one of six diets in a 2x3 design. Diets contained 0.4% Na (normotensive; NT) or 8.0% Na (hypertense; HT), and 2, 12 or 50 ug Cu/g diet. Initial body weights and mean systolic blood pressures did not differ among groups. Rats were killed when mean systolic blood pressure was 190 mm Hg. Dietary Cu had no effect on development of hypertensionmore » among the high Na groups. Dietary Cu had no effect on final body weights; however, HT rats weighed less than NT rats and had cardio- and splenomegaly and low hematocrits. The rats fed the low Cu diets had lower levels of liver, heart and plasma Cu, and ceruloplasmin oxidase (CP) activity than the other groups. The HT groups had significant increase in plasma Cu and CP activity compared to their NT counterparts. The increase in plasma CP activity was related to the increase in blood pressure. Independent of dietary Cu, the HT groups also had significant reduction in plasma Zn and increases in hepatic metallothionein and plasma cholesterol compared to the NT groups. These results support the idea that hypertension has a marked effect on Cu metabolism. The influence of this effect on vascular pathology needs to be ascertained.« less

Mechanism insight of pollutant degradation and bromate inhibition by Fe-Cu-MCM-41 catalyzed ozonation.

PubMed

Chen, Weirui; Li, Xukai; Tang, Yiming; Zhou, Jialu; Wu, Dan; Wu, Yin; Li, Laisheng

2018-03-15

A flexible catalyst, Fe-Cu-MCM-41, was employed to enhance diclofenac (DCF) mineralization and inhibit bromate formation in catalytic ozonation process. Greater TOC removal was achieved in Fe-Cu-MCM-41/O 3 process (78%) than those in Fe-MCM-41/O 3 (65%), Cu-MCM-41/O 3 (73%) and sole ozonation (42%). But it was interesting that both Cu-MCM-41/O 3 and Fe-MCM-41/O 3 achieved 93% bromate inhibition efficiency, only 71% inhibition efficiency was observed in Fe-Cu-MCM-41/O 3 . Influence of pH, TBA/NaHSO 3 and detection of by-products were conducted to explore the mechanism. By Pyridine adsorption-IR and XPS, a relationship was found among activity of catalysts, Lewis acid sites and electron transfer effect between Fe (II/III) and Cu (I/II). Fe-Cu-MCM-41 promoted ozone decomposition to generate OH, which accounted for enhanced DCF mineralization. The consumption of aqueous O 3 also suppressed the oxidative of Br - and HBrO/Br - . More HBrO/BrO - accumulated in catalytic ozonation process and less bromate generated. Bromate formation in Fe-Cu-MCM-41/O 3 process was sensitive with pH value, the acidic condition was not favor for bromate formation. Both DCF mineralization and bromate inhibition were influenced by surface reaction. Moreover, Fe-Cu-MCM-41 showed excellent catalytic performance in suppressing the accumulation of carboxylic acid, especially for oxalic acid. Nearly no oxalic acid was detected during Fe-Cu-MCM-41/O 3 process. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparison of the effect of dietary copper nanoparticles and one copper (II) salt on the copper biodistribution and gastrointestinal and hepatic morphology and function in a rat model

PubMed Central

Ognik, Katarzyna; Fotschki, Bartosz; Zduńczyk, Zenon

2018-01-01

The aim of the study was to investigate the effect of two forms (CuCO3 (CuS); and Cu nanoparticles (CuNP)) and dosages (standard 6.5 mg/kg (H), half of the standard (L)) of additional dietary Cu administered to growing rats on gastrointestinal and hepatic function and morphology. Copper in the form of CuNP vs CuS caused lower Cu faecal/urinal excretion and increased Cu accumulation in the brain tissue. Hepatic high-grade hydropic degeneration and necrotic lesions were observed only in the CuNP-H animals. In the lower gut, the dietary application of CuNP stifled bacterial enzymatic activity of caecal gut microbiota and resulted in lower SCFA production. That diminishing effect of CuNP on caecal microbiota activity was accompanied by a relative increase in the secretion of glycoside hydrolases by bacterial cells. The results showed that in comparison to Cu from CuCO3, Cu nanoparticles to a greater extent were absorbed from the intestine, accumulated in brain tissue, exerted antimicrobial effect in the caecum, and at higher dietary dose caused damages in the liver of rats. PMID:29758074

Dissociation mechanisms of HFO-1336mzz(Z) on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces: A density functional theory study

NASA Astrophysics Data System (ADS)

Huo, Erguang; Liu, Chao; Xu, Xiaoxiao; Li, Qibin; Dang, Chaobin

2018-06-01

The catalytic effect of Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces on the decomposition of HFO-1336mzz(Z) have been investigated by using Density Functional Theory (DFT) calculations. On the basis of adsorption energy analysis, the most stable adsorption energies of HFO-1336mzz(Z) and relevant products on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were studied, respectively, and the co-adsorption structures of relevant species were obtained. Finally, four initiation decomposition reactions of HFO-1336mzz(Z) on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were proposed and investigated, respectively. At the same time, the four similar homolytic reactions of free HFO-1336mzz(Z) molecular were calculated to compare with the dissociation reactions occurred on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces and illuminate the catalytic effect of Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces on the HFO-1336mzz(Z) decomposition. The results indicated that Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces had a good catalytic effect on the decomposition of HFO-1336mzz(Z). The fracture reactions of Cdbnd C bonds on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were easier to occur than that of other reactions. Cu(1 0 0) surface had the highest catalytic activity and the lowest for Cu(1 1 1) surface.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Influence of condensed species on thermo-physical properties of LTE and non-LTE SF6-Cu mixture

NASA Astrophysics Data System (ADS)

Chen, Zhexin; Wu, Yi; Yang, Fei; Sun, Hao; Rong, Mingzhe; Wang, Chunlin

2017-10-01

SF6-Cu mixture is frequently formed in high-voltage circuit breakers due to the electrode erosion and metal vapor diffusion. During the interruption process, the multiphase effect and deviation from local thermal equilibrium (non-LTE assumption) can both affect the thermo-physical of the arc plasma and further influence the performance of circuit breaker. In this paper, thermo-physical properties, namely composition, thermodynamic properties and transport coefficients are calculated for multiphase SF6-Cu mixture with and without LTE assumption. The composition is confirmed by combining classical two-temperature mass action law with phase equilibrium condition deduced from second law of thermodynamics. The thermodynamic properties and transport coefficients are calculated using the multiphase composition result. The influence of condensed species on thermo-physical properties is discussed at different temperature, pressure (0.1-10 atm), non-equilibrium degrees (1-10), and copper molar proportions (0-50%). It is found that the multiphase effect has significant influence on specific enthalpy, specific heat and heavy species thermal conductivity in both LTE and non-LTE SF6-Cu system. This paper provides a more accurate database for computational fluid dynamic calculation.

Effects of Ca, Cu, Al and La on pectin gel strength: implications for plant cell walls.

PubMed

McKenna, Brigid A; Nicholson, Timothy M; Wehr, J Bernhard; Menzies, Neal W

2010-06-16

Rheology of Ca-pectate gels is widely studied, but the behaviour of pectate gels formed by Cu, Al and La is largely unknown. It is well known that gel strength increases with increasing Ca concentration, and it is hypothesised that this would also be the case for other cations. Pectins are a critical component of plant cell walls, imparting various physicochemical properties. Furthermore, the mechanism of metal toxicity in plants is hypothesised to be, in the short term, related to metal interactions with cell wall pectin. This study investigated the influence of Ca, Cu, Al and La ion concentrations at pH 4 on the storage modulus as a function of frequency for metal-pectin gels prepared from pectin (1%) with a degree of esterification of 30%. Gels were formed in situ over 6d in metal chloride solution adjusted daily to pH 4. Cation concentration was varied to develop a relationship between gel strength and cation concentration. At similar levels of cation saturation, gel strength increased in the order of La

Influence of Donor on the Sensing Performance of a Series of Through-Bond Energy Transfer-Based Two-photon Fluorescent Cu(2+) Probes.

PubMed

Zhang, Yu-Jin; Wang, Xin; Zhou, Yong; Wang, Chuan-Kui

2016-07-01

Optical properties of a series of molecular two-photon fluorescent Cu(2+) probes containing the same acceptor (rhodamine group) are analyzed using time-dependent density functional theory in combination with analytical response theory. Special emphasis is placed on evolution of the probes' optical properties in the presence of Cu(2+) . In this study, the compound with naphthalene as the donor is shown to be excellent ratiometric fluorescent chemosensor, whereas the compound with quinoline derivative as the donor shows off/on-typed colorimetric fluorescent response. For the compound with naphthalimide derivative as the donor, changing the connection between the donor and acceptor can efficiently prevent the fluorescent quenching of the probe both in the absence and presence of Cu(2+) . The donor moiety and the connection between donor and acceptor are thus found to play dominant roles on sensing performance of these probes. Moreover, distributions of molecular orbitals involved in the excitation and emission of the probes are analyzed to explore responsive mechanism of the probes. The through-bond energy transfer process is theoretically demonstrated. Our results are used to elucidate the available experimental measurements. This work is helpful to understand the relationships of structure with optical properties for the studied probes. © 2016 The American Society of Photobiology.

CH4 dissociation in the early stage of graphene growth on Fe-Cu(100) surface: Theoretical insights

NASA Astrophysics Data System (ADS)

Tian, Baoyang; Liu, Tianhui; Yang, YanYan; Li, Kai; Wu, Zhijian; Wang, Ying

2018-01-01

The mechanism of CH4 dissociation and carbon nucleation process on the Fe doped Cu(100) surface were investigated systematically by using the density functional theory (DFT) calculations and microkinetic model. The activity of the Cu(100) surface was improved by the doped Fe atom and the atomic Fe on the Fe-Cu(100) surface was the reaction center due to the synergistic effect. In the dissociation process of CH4, CH3 → CH2 + H was regarded as the rate-determining step. The results obtained from the microkinetic model showed that the coverage of CHx(x = 1-3) was gradually decreased with the temperature increasing and CH3 was always the major intermediate at the broad range of the temperature (from 1035 to 1080 °C) and the ratio of H2/CH4 (from 0 to 5). It is also found that the reaction rates were increased with the temperature increasing. However, the reaction rates were reduced (or increased) at the range of H2/CH4 = 0-0.2 (or H2/CH4 > 0.2). It is noted that controlling the H2 partial pressure was an effective method to regulate the major intermediates and reaction rates of CH4 dissociation and further influence the growing process of graphene.

Room-temperature preparation of trisilver-copper-sulfide/polymer based heterojunction thin film for solar cell application

NASA Astrophysics Data System (ADS)

Lei, Yan; Yang, Xiaogang; Gu, Longyan; Jia, Huimin; Ge, Suxiang; Xiao, Pin; Fan, Xiaoli; Zheng, Zhi

2015-04-01

Solar cells devices based on inorganic/polymer heterojunction can be a possible solution to harvest solar energy and convert to electric energy with high efficiency through a cost-effective fabrication. The solution-process method can be easily used to produce large area devices. Moreover, due to the intrinsic different charge separation, diffusion or recombination in various semiconductors, the interfaces between each component may strongly influence the inorganic/polymer heterojunction performance. Here we prepared a n-type Ag3CuS2 (Eg = 1.25 eV) nanostructured film through a room-temperature element reaction process, which was confirmed as direct bandgap semiconductor through density function theory simulation. This Ag3CuS2 film was spin-coated with an organic semiconducting poly(3-hexythiophene) (P3HT) or polythieno[3,4-b]-thiophene-co-benzodithiophene (PTB7) film, which formed an inorganic/polymer heterojunction. After constructing it to a solar cell device, the power conversion efficiencies of 0.79% and 0.31% were achieved with simulated solar illumination on Ag3CuS2/P3HT and Ag3CuS2/PTB7, respectively. A possible mechanism was discussed and we showed the charge separation at interface of inorganic and polymer semiconductors played an important role.

Electrochemical fabrication and optoelectronic properties of hybrid heterostructure of CuPc/porous GaN

NASA Astrophysics Data System (ADS)

Peng, Fei; Qin, Shuang-Jiao; Hu, Li-Feng; Wang, Juan-Ye; Yang, Jia-Mei; Chen, Xue-Qing; Pan, Ge-Bo

2016-05-01

A new hybrid heterostructure of p-type copper phthalocyanine (CuPc) and n-type porous GaN (PGaN) has been fabricated by electrophoretic deposition. The influence of CuPc concentration, electric field intensity, and deposition time on the growth of CuPc film has been explored. The as-prepared CuPc films are made of numerous nanorods. The X-ray diffraction (XRD) spectra revealed that the CuPc films are the β phase and amorphous type on pristine and porous GaN, respectively. Moreover, the prototype devices were fabricated on the basis of the CuPc/PGaN heterostructures. The devices exhibited excellent photodetector performance under ultraviolet (UV) light illumination.

The Apparent Contact Angle and Wetted Area of Active Alloys on Silicon Carbide as a Function of the Temperature and the Surface Roughness: A Multivariate Approach

NASA Astrophysics Data System (ADS)

Tillmann, Wolfgang; Pfeiffer, Jan; Wojarski, Lukas

2015-08-01

Despite the broad field of applications for active filler alloys for brazing ceramics, as well as intense research work on the wetting and spreading behavior of these alloys on ceramic surfaces within the last decades, the manufactured joints still exhibit significant variations in their properties due to the high sensitivity of the alloys to changing brazing conditions. This increases the need for investigations of the wetting and spreading behavior of filler alloys with regard to the dominating influences combined with their interdependencies, instead of solely focusing on single parameter investigations. In this regard, measurements of the wetting angle and area were conducted at solidified AgCuTi and CuSnTi alloys on SiC substrates. Based on these measurements, a regression model was generated, illustrating the influence of the brazing temperature, the roughness of the faying surfaces, the furnace atmosphere, and their interdependencies on the wetting and spreading behavior of the filler alloys. It was revealed that the behavior of the melts was significantly influenced by the varied brazing parameters, as well as by their interdependencies. This result was also predicted by the developed model and showed a high accuracy.

Theoretical and experimental studies on wide-band-gap p-type conductive BaCuSeF and related compounds

NASA Astrophysics Data System (ADS)

Sakakima, Hiroshi; Nishitani, Mikihiko; Yamamoto, Koichi; Wada, Takahiro

2015-08-01

BaCuSeF and related compounds, MCuQF (M = Ba, Sr; Q = Se, S), are known to show p-type conduction. The formation energies of the Cu vacancy ΔH[VCu] in a MCuQF system were computed by first-principles calculation with a generalized gradient approximation (GGA) of the Perdew-Burke-Ernzerhof (PBE) functional as an electron exchange and correlation functional. The density of states (DOS) of BaCuSeF was calculated with the hybrid functional of Heyd-Scuseria-Ernzerhof (HSE) 06. ΔH[VCu] was found to be very small under both the Cu- and Q-rich conditions, which probably contributes to p-type conduction. The electronic structure of BaCuSeF was studied by X-ray photoelectron spectroscopy (XPS) with UV photoelectron yield spectroscopy (UVPYS) and photoemission yield spectroscopy (PYS). The determined depth of the top of the valence band relative to the vacuum level was about 4.9 eV. This value is desirable for applications in compound semiconductor thin-film tandem solar cells since the absorbers of polycrystalline thin-film solar cells, such as CdTe and Cu(In,Ga)Se2, are p-type semiconductors. The DOS of BaCuSeF calculated with the HSE06 functional was almost consistent with the XPS spectrum.

Interactions between suspension characteristics and physicochemical properties of silver and copper oxide nanoparticles: a case study for optimizing nanoparticle stock suspensions using a central composite design.

PubMed

Son, Jino; Vavra, Janna; Li, Yusong; Seymour, Megan; Forbes, Valery

2015-04-01

The preparation of a stable nanoparticle stock suspension is the first step in nanotoxicological studies, but how different preparation methods influence the physicochemical properties of nanoparticles in a solution, even in Milli-Q water, is often under-appreciated. In this study, a systematic approach using a central composite design (CCD) was employed to investigate the effects of sonication time and suspension concentration on the physicochemical properties (i.e. hydrodynamic diameter, zeta potential and ion dissolution) of silver (Ag) and copper oxide (CuO) nanoparticles (NPs) and to identify optimal conditions for suspension preparation in Milli-Q water; defined as giving the smallest particle sizes, highest suspension stability and lowest ion dissolution. Indeed, all the physicochemical properties of AgNPs and CuONPs varied dramatically depending on how the stock suspensions were prepared and differed profoundly between nanoparticle types, indicating the importance of suspension preparation. Moreover, the physicochemical properties of AgNPs and CuONPs, at least in simple media (Milli-Q water), behaved in predictable ways as a function of sonication time and suspension concentration, confirming the validity of our models. Overall, the approach allows systematic assessment of the influence of various factors on key properties of nanoparticle suspensions, which will facilitate optimization of the preparation of nanoparticle stock suspensions and improve the reproducibility of nanotoxicological results. We recommend that further attention be given to details of stock suspension preparation before conducting nanotoxicological studies as these can have an important influence on the behavior and subsequent toxicity of nanoparticles. Copyright © 2014 Elsevier Ltd. All rights reserved.

Spectroscopic interaction studies of substituted and unsubstituted copper phthalocyanine with adsorbed organic vapours

NASA Astrophysics Data System (ADS)

Ridhi, R.; Kang, Jasmeen; Saini, G. S. S.; Tripathi, S. K.

2018-05-01

The present study deals with comparing the interaction mechanism of adsorbed organic vapours with Copper Phthalocyanine thin films in its substituted and unsubstituted forms. For this purpose, the variations in vibrational levels of substituted CuPc (CuPcS) functionalized with tetrasulfonic acid tetrasodium salt and unsubstituted CuPc after exposure with methanol and benzene vapours is analyzed. Fourier transform infrared (FTIR) is used to study the interaction behaviour. The bulkier group tetrasulfonic acid tetrasodium salt added to CuPc leads to occupation of more space in the molecular arrangement as compared to unsubstituted CuPc and hence alteration of its properties. FTIR spectra of CuPc and CuPcS before and after vapours exposures highlighted the effect of these vapours on the various bonds and the role of functional group in altering the molecular structure of CuPcS during interaction with adsorbed vapours.

N-Terminal Cu-Binding Motifs (Xxx-Zzz-His, Xxx-His) and Their Derivatives: Chemistry, Biology and Medicinal Applications.

PubMed

Gonzalez, Paulina; Bossak, Karolina; Stefaniak, Ewelina; Hureau, Christelle; Raibaut, Laurent; Bal, Wojciech; Faller, Peter

2018-06-07

Peptides and proteins with N-terminal amino acid sequences NH 2 -Xxx-His (XH) and NH 2 -Xxx-Zzz-His (XZH) form well-established high-affinity Cu II -complexes. Key examples are Asp-Ala-His (in serum albumin) and Gly-His-Lys, the wound healing factor. This opens a straightforward way to add a high-affinity Cu II -binding site to almost any peptide or protein, by chemical or recombinant approaches. Thus, these motifs, NH 2 -Xxx-Zzz-His in particular, have been used to equip peptides and proteins with a multitude of functions based on the redox activity of Cu, including nuclease, protease, glycosidase, or oxygen activation properties, useful in anticancer or antimicrobial drugs. More recent research suggests novel biological functions, mainly based on the redox inertness of Cu II in XZH, like PET imaging (with 64 Cu), chelation therapies (for instance in Alzheimer's disease and other types of neurodegeneration), antioxidant units, Cu transporters and activation of biological functions by strong Cu II binding. This Review gives an overview of the chemical properties of Cu-XH and -XZH motifs and discusses the pros and cons of the vastly different biological applications, and how they could be improved depending on the application. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Rudeck, P.J.; Harper, J.M.E.; Fryer, P.M.

The copper concentration in aluminum-copper alloys can be altered by ion bombardment during film deposition. We have measured the sputtering yields of aluminum and copper in Al-Cu alloys as a function of the Cu concentration (5--13 at. %) and the angle of ion incidence (0/sup 0/--40/sup 0/ from normal). During deposition, the films were partially resputtered by 500 eV Ar/sup +/ ion bombardment from a Kaufman ion source. We found that the Cu sputtering yield decreases by up to a factor of 10 in the alloy, relative to elemental Cu. The Al sputtering yield remains close to the elemental value.more » The net effect is a strong preferential sputtering of Al relative to Cu, which enhances the Cu concentration in an ion-bombarded film. The Al/Cu sputtering yield ratio for normal incidence ion bombardment ranges from 3 to 5 as a function of Cu concentration. This ratio decreases with increasing angle of incidence to as low as 2 for 40/sup 0/ incident ions. However, since a higher fraction of the film is resputtered from a sloping surface, a higher Cu concentration is found on a sloping surface relative to a flat surface. These results show that the film composition will vary as a function of the surface topography.« less

Electrical transport properties of CuXSn1-X metallic glasses

NASA Astrophysics Data System (ADS)

Vora, A. M.; Gajjar, P. N.

2018-05-01

In the present paper, we report the electrical resistivity (ρ), the thermoelectric power (TEP) and thermal conductivity (σ) of CuXSn1-X metallic glasses computed from Faber-Ziman formulation with Percus-Yevic (PY) hard sphere structure factors of Ashcroft and Langreth. Our well-recognized model potential is used to represent ionic interaction for the first time with seven local field correction functions due to Hartree (H), Hubbard-Sham (HS), Vashishta-Singwi (VS), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) in the present computation and found suitable for such study. The percentile influence of various local field corrections with respect to Hartree (H) is found in the range of 17.35%-71.55%. It is concluded that, the comparison of present and experimental findings of electrical resistivity (ρ) is highly promising.

[Donor age affects on the «behavior» and the sensibility bone marrow cells in on copper ion of the primary culture].

PubMed

Bozhkov, A I; Ohiienko, S L; Kuznetsova, Yu A; Bondar', A Yu; Marchenko, V P; Gumennaya, M S

2017-01-01

The changes of bone marrow cells (BMC) number in the primary culture from 0 to 96 hours, the pattern (the distribution of cells) of cells morphotypes and «lifespan» (the time of cell life after isolation) of myelocytes, metamyelocytes, band and segmented neutrophils, isolated of the young (3 months) and old (20months) animals, were investigated. The number of the BMC obtained from intact old animals increased faster in primary culture, than from young animals. The Cu induced fibrosis had different influence on the rate of BMC culture growth of old and young animals. The adding of 4 mM and 8 mM CuSO4x5H2O in the BMC culture of young and old animals resulted in a dose-dependent inhibition of growth rate of young animal cells. If copper ions were added into the culture of BMC of old animals, the decreased of the BMC number was described less than for cells of young animals. The adding of 8 mM CuSO4x5H2O inhibited proliferation less, than the adding of 4 mM CuSO4x5H2O. The Cu-induced liver fibrosis had accelerated the BMC rate death of both old and young animals. However, this effect was more pronounced in young animals. It is suggested, that during the ontogenesis the BMC undergo such epigenetic changes, which change functional properties.

Cyanobacteria as test organisms and biosorbents

NASA Astrophysics Data System (ADS)

Fokina, A. I.; Ogorodnikova, S. Yu.; Domracheva, L. I.; Lyalina, E. I.; Gornostaeva, E. A.; Ashikhmina, T. Ya.; Kondakova, L. V.

2017-01-01

Bioassay and biosorption potentials of different groups of cyanobacteria ( CB)— Nostoc linckia (Roth.) Born. et Flah. No. 271, natural biofilms dominated by CB of Phormidium genus, and biofilms dominated by Nostoc commune (Vauch. Elenk)—were estimated. The physiological-biochemical response of CB to the influence of copper sulfate (II) (catalase activity with a gasometric method and dehydrogenase activity, lipid peroxidation, and chlorophyll ɑ and pheophytin contents with a spectrophotometric method) was studied; metal bioaccumulation was determined with a stripping voltammetry method. It was found that the communities dominated by Phormidium genus (CB biomass 0.2 g/dm3) removed copper compounds from the solutions with Cu2+ ion concentration of 20 mg/dm3 almost completely (by 99%); communities dominated by CB N. commune, by 87%; and pure culture of N. linckia, by 50%. Dehydrogenase and catalase activities and the intensity of bioluminescence proved to be sensitive indicators of the response of CB to Cu2+ ions. The impact of Cu2+ ions (20 mg/dm3) on a biofilm dominated by CB of Phormidium genus resulted in the fivefold decrease of catalase activity during 24 h; dehydrogenase activity decreased by nearly 357 times. The bioluminescence intensity during 24 h decreased by 1.3-100 times under the impact of Cu2+ (2 mg/dm3) and by 8.6-200 times in variants with a higher concentration of Cu2+ (20 mg/dm3). This regularity can be used as a test function in bioassay.

Redox-switchable copper(I) metallogel: a metal-organic material for selective and naked-eye sensing of picric acid.

PubMed

Sarkar, Sougata; Dutta, Soumen; Chakrabarti, Susmita; Bairi, Partha; Pal, Tarasankar

2014-05-14

Thiourea (TU), a commercially available laboratory chemical, has been discovered to introduce metallogelation when reacted with copper(II) chloride in aqueous medium. The chemistry involves the reduction of Cu(II) to Cu(I) with concomitant oxidation of thiourea to dithiobisformamidinium dichloride. The gel formation is triggered through metal-ligand complexation, i.e., Cu(I)-TU coordination and extensive hydrogen bonding interactions involving thiourea, the disulfide product, water, and chloride ions. Entangled network morphology of the gel selectively develops in water, maybe for its superior hydrogen-bonding ability, as accounted from Kamlet-Taft solvent parameters. Complete and systematic chemical analyses demonstrate the importance of both Cu(I) and chloride ions as the key ingredients in the metal-organic coordination gel framework. The gel is highly fluorescent. Again, exclusive presence of Cu(I) metal centers in the gel structure makes the gel redox-responsive and therefore it shows reversible gel-sol phase transition. However, the reversibility does not cause any morphological change in the gel phase. The gel practically exhibits its multiresponsive nature and therefore the influences of different probable interfering parameters (pH, selective metal ions and anions, selective complexing agents, etc.) have been studied mechanistically and the results might be promising for different applications. Finally, the gel material shows a highly selective visual response to a commonly used nitroexplosive, picric acid among a set of 19 congeners and the preferred selectivity has been mechanistically interpreted with density functional theory-based calculations.

Fabrication of Cu-Ag core-shell bimetallic superfine powders by eco-friendly reagents and structures characterization

NASA Astrophysics Data System (ADS)

Zhao, Jun; Zhang, Dongming; Zhao, Jie

2011-09-01

Superfine bimetallic Cu-Ag core-shell powders were synthesized by reduction of copper sulfate pentahydrate and silver nitrate with eco-friendly ascorbic acid as a reducing agent and cyclodextrins as a protective agent in an aqueous system. The influence of Ag/Cu ratio on coatings was investigated. Ag was homogeneously distributed on the surface of Cu particles at a mole ratio of Ag/Cu=1. FE-SEM showed an uniformity of Ag coatings on Cu particles. Antioxidation of Cu particles was improved by increasing Ag/Cu ratio. TEM-EDX and UV-vis spectra also revealed that Cu cores were covered by Ag nanoshells on the whole. The surface composition analysis by XPS indicated that only small parts of Cu atoms in the surface were oxidized. It was noted that the hindrance of cyclodextrins chemisorbed on particles plays an important role in forming high quality and good dispersity Cu-Ag (Cu@Ag) core-shell powders.

Disorganized Amygdala Networks in Conduct-Disordered Juvenile Offenders With Callous-Unemotional Traits.

PubMed

Aghajani, Moji; Klapwijk, Eduard T; van der Wee, Nic J; Veer, Ilya M; Rombouts, Serge A R B; Boon, Albert E; van Beelen, Peter; Popma, Arne; Vermeiren, Robert R J M; Colins, Olivier F

2017-08-15

The developmental trajectory of psychopathy seemingly begins early in life and includes the presence of callous-unemotional (CU) traits (e.g., deficient emotional reactivity, callousness) in conduct-disordered (CD) youth. Though subregion-specific anomalies in amygdala function have been suggested in CU pathophysiology among antisocial populations, system-level studies of CU traits have typically examined the amygdala as a unitary structure. Hence, nothing is yet known of how amygdala subregional network function may contribute to callous-unemotionality in severely antisocial people. We addressed this important issue by uniquely examining the intrinsic functional connectivity of basolateral amygdala (BLA) and centromedial amygdala (CMA) networks across three matched groups of juveniles: CD offenders with CU traits (CD/CU+; n = 25), CD offenders without CU traits (CD/CU-; n = 25), and healthy control subjects (n = 24). We additionally examined whether perturbed amygdala subregional connectivity coincides with altered volume and shape of the amygdaloid complex. Relative to CD/CU- and healthy control youths, CD/CU+ youths showed abnormally increased BLA connectivity with a cluster that included both dorsal and ventral portions of the anterior cingulate and medial prefrontal cortices, along with posterior cingulate, sensory associative, and striatal regions. In contrast, compared with CD/CU- and healthy control youths, CD/CU+ youths showed diminished CMA connectivity with ventromedial/orbitofrontal regions. Critically, these connectivity changes coincided with local hypotrophy of BLA and CMA subregions (without being statistically correlated) and were associated to more severe CU symptoms. These findings provide unique insights into a putative mechanism for perturbed attention-emotion interactions, which could bias salience processing and associative learning in youth with CD/CU+. Copyright © 2016 Society of Biological Psychiatry. Published by Elsevier Inc. All rights reserved.

Analysis of the Influence of Starting Materials and Processing Conditions on the Properties of W/Cu Alloys.

PubMed

Montealegre-Meléndez, Isabel; Arévalo, Cristina; Perez-Soriano, Eva M; Neubauer, Erich; Rubio-Escudero, Cristina; Kitzmantel, Michael

2017-02-08

In this work, a study of the influence of the starting materials and the processing time used to develop W/Cu alloys is carried out. Regarding powder metallurgy as a promising fabrication route, the difficulties in producing W/Cu alloys motivated us to investigate the influential factors on the final properties of the most industrially demanding alloys: 85-W/15-Cu, 80-W/20-Cu, and 75-W/25-Cu alloys. Two different tungsten powders with large variation among their particle size-fine (W f ) and coarse (W c ) powders-were used for the preparation of W/Cu alloys. Three weight ratios of fine and coarse (W f :W c ) tungsten particles were analyzed. These powders were labelled as "tungsten bimodal powders". The powder blends were consolidated by rapid sinter pressing (RSP) at 900 °C and 150 MPa, and were thus sintered and compacted simultaneously. The elemental powders and W/Cu alloys were studied by optical microscopy (OM) and scanning electron microscopy (SEM). Thermal conductivity, hardness, and densification were measured. Results showed that the synthesis of W/Cu using bimodal tungsten powders significantly affects the final alloy properties. The higher the tungsten content, the more noticeable the effect of the bimodal powder. The best bimodal W powder was the blend with 10 wt % of fine tungsten particles (10-W f :90-W c ). These specimens present good values of densification and hardness, and higher values of thermal conductivity than other bimodal mixtures.

Analysis of the Influence of Starting Materials and Processing Conditions on the Properties of W/Cu Alloys

PubMed Central

Montealegre-Meléndez, Isabel; Arévalo, Cristina; Perez-Soriano, Eva M.; Neubauer, Erich; Rubio-Escudero, Cristina; Kitzmantel, Michael

2017-01-01

In this work, a study of the influence of the starting materials and the processing time used to develop W/Cu alloys is carried out. Regarding powder metallurgy as a promising fabrication route, the difficulties in producing W/Cu alloys motivated us to investigate the influential factors on the final properties of the most industrially demanding alloys: 85-W/15-Cu, 80-W/20-Cu, and 75-W/25-Cu alloys. Two different tungsten powders with large variation among their particle size—fine (Wf) and coarse (Wc) powders—were used for the preparation of W/Cu alloys. Three weight ratios of fine and coarse (Wf:Wc) tungsten particles were analyzed. These powders were labelled as “tungsten bimodal powders”. The powder blends were consolidated by rapid sinter pressing (RSP) at 900 °C and 150 MPa, and were thus sintered and compacted simultaneously. The elemental powders and W/Cu alloys were studied by optical microscopy (OM) and scanning electron microscopy (SEM). Thermal conductivity, hardness, and densification were measured. Results showed that the synthesis of W/Cu using bimodal tungsten powders significantly affects the final alloy properties. The higher the tungsten content, the more noticeable the effect of the bimodal powder. The best bimodal W powder was the blend with 10 wt % of fine tungsten particles (10-Wf:90-Wc). These specimens present good values of densification and hardness, and higher values of thermal conductivity than other bimodal mixtures. PMID:28772502

Application of EDTA-functionalized bamboo activated carbon (BAC) for Pb(II) and Cu(II) removal from aqueous solutions

NASA Astrophysics Data System (ADS)

Lv, Dan; Liu, Yu; Zhou, Jiasheng; Yang, Kunlun; Lou, Zimo; Baig, Shams Ali; Xu, Xinhua

2018-01-01

In this study, a novel bamboo activated carbon (BAC) with ethylene diamine tetraacetic acid (EDTA) functionality was prepared by direct grafting in the presence of tetraethyl orthosilicate (TEOS) as a crosslinking agent. The BAC@SiO2-EDTA was characterized by SEM, TEM, TGA, FTIR, XPS and its adsorption property for removal of Pb(II) and Cu(II) under various experimental conditions was also investigated. The characterization results reflected that EDTA was successfully assembled on the surface of the BAC and average pore size increased from 4.10 to 4.83 nm as BAC grafted with EDTA. Adsorption data fitted very well in Langmuir isotherm model and pseudo-second-order kinetic model. As compared with the raw BAC, the maximum adsorption capacities of BAC@SiO2-EDTA for the Pb(II) and Cu(II) increased from 45.45 to 123.45 mg g-1 and from 6.85 to 42.19 mg g-1, since the existence of EDTA on modified BAC promoted the formation of chemical complex. The removal of heavy metal ions mainly depended on the complexation with EDTA and the electrostatic attractions with negatively charged surface of BAC@SiO2-EDTA. The adsorption of Pb(II)/Cu(II) on the BAC@SiO2-EDTA was pH dependent and pH 5-6 was considered an optimum. However, lower temperature favored the adsorption and the maximum adsorption was recorded at 20 °C. In addition, BAC@SiO2-EDTA had an excellent reusability with about 40% decline in the adsorption capacity for Pb(II) after fifth reuse. Insignificant influences of co-existing cations and natural organic matter (NOM) were found on the adsorption of Pb(II) and Cu(II). All the results demonstrate that BAC@SiO2-EDTA is a potential adsorbent for metal ions in wastewater.

Effect of pre-pyrolysis mode on simultaneous introduction of nitrogen/oxygen-containing functional groups into the structure of bagasse-based mesoporous carbon and its influence on Cu(II) adsorption.

PubMed

Wan, Zeqing; Li, Kunquan

2018-03-01

A convenient effective microwave pre-pyrolysis treatment to synthesize biomass-based mesoporous carbon with higher nitrogen/oxygen-chelating adsorption for Cu(II) is reported here, in which phosphoric acid impregnated bagasse was used as a microwave absorber and porogen. For comparison, conventional electric-heating pyrolyzed carbon was prepared and doped with nitrogen/oxygen groups. Nitrogen adsorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) and batch adsorption were employed to investigate the effects of the two pre-pyrolysis modes on the sample physicochemical and Cu(II) adsorptive properties. The 22-min-microwave-pyrolyzed bagasse mesoporous activated carbon (MBAC, 85.32% mesoporosity) contained 10.52% O, which is 3.94% more than electric-heating pyrolyzed mesoporous activated carbon (89.52% mesoporosity). After electrophilic aromatic substitutions of N/O doping, the former possessed more N (5.83%) and more O (21.40%), confirming that time-saving energy-efficient microwave pyrolysis favors the formation of defective C/O atoms in or at the edges of the graphite layer of MBAC, which are highly active and tend to act as preferred reactive positions for the doping of N/O-containing groups simultaneously compared with conventional electric-heating pyrolysis. These N and O species existed mainly as COOH, OH, NH and NH 2 functional groups, and were confirmed by XPS to be active sites for metal binding via electrostatic attraction, hydrogen bonding, a chelate effect and complexation, resulting in the great enhancement of Cu(II) adsorption. Langmuir isotherm and pseudo-second-order kinetic fitting further proved that Cu(II) adsorption by N/O-doped MBAC is ascribed mainly to chemisorption. Therefore, rapid microwave pre-pyrolysis provides a promising route to prepare excellent-performance N/O-doped carbon adsorbents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Alteration of intracellular protein expressions as a key mechanism of the deterioration of bacterial denitrification caused by copper oxide nanoparticles.

PubMed

Su, Yinglong; Zheng, Xiong; Chen, Yinguang; Li, Mu; Liu, Kun

2015-10-28

The increasing production and utilization of copper oxide nanoparticles (CuO NPs) result in the releases into the environment. However, the influence of CuO NPs on bacterial denitrification, one of the most important pathways to transform nitrate to dinitrogen in environment, has seldom been studied. Here we reported that CuO NPs caused a significant alteration of key protein expressions of a model denitrifier, Paracoccus denitrificans, leading to severe inhibition to denitrification. Total nitrogen removal efficiency was decreased from 98.3% to 62.1% with the increase of CuO NPs from 0.05 to 0.25 mg/L. Cellular morphology and integrity studies indicated that nanoparticles entered the cells. The proteomic bioinformatics analysis showed that CuO NPs caused regulation of proteins involved in nitrogen metabolism, electron transfer and substance transport. The down-regulation of GtsB protein (responsible for glucose transport) decreased the production of NADH (electron donor for denitrification). Also, the expressions of key electron-transfer proteins (including NADH dehydrogenase and cytochrome) were suppressed by CuO NPs, which adversely affected electrons transfer for denitrification. Further investigation revealed that CuO NPs significantly inhibited the expressions and catalytic activities of nitrate reductase and nitrite reductase. These results provided a fundamental understanding of the negative influences of CuO NPs on bacterial denitrification.

Alteration of intracellular protein expressions as a key mechanism of the deterioration of bacterial denitrification caused by copper oxide nanoparticles

PubMed Central

Su, Yinglong; Zheng, Xiong; Chen, Yinguang; Li, Mu; Liu, Kun

2015-01-01

The increasing production and utilization of copper oxide nanoparticles (CuO NPs) result in the releases into the environment. However, the influence of CuO NPs on bacterial denitrification, one of the most important pathways to transform nitrate to dinitrogen in environment, has seldom been studied. Here we reported that CuO NPs caused a significant alteration of key protein expressions of a model denitrifier, Paracoccus denitrificans, leading to severe inhibition to denitrification. Total nitrogen removal efficiency was decreased from 98.3% to 62.1% with the increase of CuO NPs from 0.05 to 0.25 mg/L. Cellular morphology and integrity studies indicated that nanoparticles entered the cells. The proteomic bioinformatics analysis showed that CuO NPs caused regulation of proteins involved in nitrogen metabolism, electron transfer and substance transport. The down-regulation of GtsB protein (responsible for glucose transport) decreased the production of NADH (electron donor for denitrification). Also, the expressions of key electron-transfer proteins (including NADH dehydrogenase and cytochrome) were suppressed by CuO NPs, which adversely affected electrons transfer for denitrification. Further investigation revealed that CuO NPs significantly inhibited the expressions and catalytic activities of nitrate reductase and nitrite reductase. These results provided a fundamental understanding of the negative influences of CuO NPs on bacterial denitrification. PMID:26508362

CuY zeolite catalysts prepared by ultrasonication-assisted ion-exchange for oxidative carbonylation of methanol to dimethyl carbonate.

PubMed

Woo, Je-Min; Seo, Jung Yoon; Kim, Hyunuk; Lee, Dong-Ho; Park, Young Cheol; Yi, Chang-Keun; Park, Yeong Seong; Moon, Jong-Ho

2018-06-01

The influence of ultrasonication treatment on the catalytic performance of CuY zeolite catalysts was investigated for the liquid-phase oxidative carbonylation of methanol to dimethyl carbonate (DMC). The deammoniation method of NH 4 Y into HY zeolites was optimized and characterized by elemental analyzer, derivative thermogravimetry, Brunauer-Emmett-Teller (BET) analyzer, and powder X-ray diffractometry, revealing that the HY zeolite deammoniated at 400 °C presented the highest surface area, complete ammonium/proton ion exchange, and no structure collapse, rendering it the best support from all the prepared zeolites. CuY zeolites were prepared via aqueous phase ion exchange with the aid of ultrasonication. Upon ultrasonication, the Cu + active centers were uniformly dispersed in the Y zeolites, penetrating the core of the zeolite particles in a very short time. In addition to enhancing the Cu dispersity, the ultrasonication treatment influenced the BET surface area, acid amount, Cu + /Cu 2+ ratio, and also had a relatively small impact on the Cu loading. Consequently, adequate exposure to ultrasonication was able to increase the conversion rate of methanol into dimethyl carbonate up to 11.4% with a comparable DMC selectivity of 23.7%. This methanol conversion is 2.65 times higher than that obtained without the ultrasonication treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

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

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

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

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

Algorithm based on the Thomson problem for determination of equilibrium structures of metal nanoclusters

NASA Astrophysics Data System (ADS)

Arias, E.; Florez, E.; Pérez-Torres, J. F.

2017-06-01

A new algorithm for the determination of equilibrium structures suitable for metal nanoclusters is proposed. The algorithm performs a stochastic search of the minima associated with the nuclear potential energy function restricted to a sphere (similar to the Thomson problem), in order to guess configurations of the nuclear positions. Subsequently, the guessed configurations are further optimized driven by the total energy function using the conventional gradient descent method. This methodology is equivalent to using the valence shell electron pair repulsion model in guessing initial configurations in the traditional molecular quantum chemistry. The framework is illustrated in several clusters of increasing complexity: Cu7, Cu9, and Cu11 as benchmark systems, and Cu38 and Ni9 as novel systems. New equilibrium structures for Cu9, Cu11, Cu38, and Ni9 are reported.

Algorithm based on the Thomson problem for determination of equilibrium structures of metal nanoclusters.

PubMed

Arias, E; Florez, E; Pérez-Torres, J F

2017-06-28

A new algorithm for the determination of equilibrium structures suitable for metal nanoclusters is proposed. The algorithm performs a stochastic search of the minima associated with the nuclear potential energy function restricted to a sphere (similar to the Thomson problem), in order to guess configurations of the nuclear positions. Subsequently, the guessed configurations are further optimized driven by the total energy function using the conventional gradient descent method. This methodology is equivalent to using the valence shell electron pair repulsion model in guessing initial configurations in the traditional molecular quantum chemistry. The framework is illustrated in several clusters of increasing complexity: Cu 7 , Cu 9 , and Cu 11 as benchmark systems, and Cu 38 and Ni 9 as novel systems. New equilibrium structures for Cu 9 , Cu 11 , Cu 38 , and Ni 9 are reported.

Sorption and biodegradability of sludge bacterial extracellular polymers in soil and their influence on soil copper behavior.

PubMed

Zhou, L X; Zhou, S G; Zhan, X H

2004-01-01

Bacterial extracellular polymers (BEP) affect the translocation and fate of organic and inorganic pollutants in terrestrial and aquatic ecosystems. In this study, BEP from activated sludge was compared with sludge dissolved organic matter (DOM) in terms of behavior and effects on the mobilization and bioavailability of Cu in a well-aged Cu-contaminated orchard sandy loam. Addition of sludge BEP (10-200 mg dissolved organic carbon [DOC] L(-1)) to the soil resulted in 1.6- to 12.8-fold-higher soil soluble Cu concentration over the control and 1.3- to 2.2-fold over sludge DOM of the same concentration. Consequently, the Cu uptake by the ryegrass (Lolium perenne L., cv. Target) grown in the soil was increased by 31% due to interval watering of 100 mg DOC L(-1) of sludge BEP solution in a 35-d period. The influence of sludge BEP on mobilizing soil Cu could be maintained as long as 60 d or more, depending on BEP biodegradation status. The findings that sludge BEP promoted Cu mobilization and bioavailability could be attributed to less adsorption of BEP by soil, slow degradation, and higher affinity with Cu. For example, after 3 wk of aerobic incubation, the soluble Cu present in the sludge DOM-treated soil was reduced to about the level of the control, while the concentration of soluble Cu in BEP-treated soil was 6.2 times higher than that in the control. Therefore, sludge BEP could act as a facilitated-transport carrier of Cu. The environmental risk of Cu should receive much attention if BEP is incorporated into soils.

Influence of nanoparticle concentration on thermo-physical properties of CuO-propylene glycol nanofluids.

PubMed

Suganthi, Kuppusamy Swaminathan; Radhakrishnan, Anju K; Anusha, Natarajan; Rajan, Kalpoondi Sekar

2014-06-01

Experiments were performed on the preparation and characterization of CuO-propylene glycol nanofluids. The influence of nanoparticle concentration and temperature on nanofluid viscosity reveals existence of a range of nanoparticle concentration and temperature in which the viscosity of nanofluid is lower than that of propylene glycol, possibly due to interactions between nanoparticles and propylene glycol. A temperature-independent, thermal conductivity enhancement of 38% was obtained for nanoparticle concentration of 1.5 vol% over a temperature range of 10-60 degrees C. We believe that particle clustering contributes to the thermal conductivity enhancement in CuO-propylene glycol nanofluids.

[Catalytic combustion of soot on combined oxide catalysts].

PubMed

He, Xu-wen; Yu, Jun-jie; Kang, Shou-fang; Hao, Zheng-ping; Hu, Chun

2005-01-01

Combined oxide catalysts are prepared for catalytic combustion of soot and regeneration from diesel emissions. Thermo-gravimetric analysis(TGA) and temperature programmed oxidation(TPO)are used to evaluate the activity of catalysts under the influence of composition,atomic ration, H2O, calcinations temperature and mass ration between catalysts and soot. Results show that Cu-Mo-O had high activity among double metal oxide catalysts. Among multicomponent metal oxide catalysts, Cu-K-Mo-O had high activity when atomic ratio Cu: K: Mo = 1:1:2 and mass ration between catalysts and soot equals 5: 1. Under this condition, soot ignition temperature of Cu-K-Mo-O catalyst was 327 degrees C. H2O addition and calcinations temperature had little influence on it,which is one kind of compatible catalyst for soot control and catalytic regeneration from diesel emissions.

Synthesis, characterization and experimental investigation of Cu-BTC as CO2 adsorbent from flue gas.

PubMed

Xie, Jiangkun; Yan, Naiqiang; Qu, Zan; Yang, Shijian

2012-01-01

Porous Cu-BTC material was synthesized by the solvothermal method. Powder X-ray diffraction (PXRD) was used to test the phase purity of the synthesized material and investigate its structural stability under the influence of flue gas components. The thermal stability of the material was determined through thermal gravimetric (TG) analysis. Scanning electron microscopy (SEM) was employed to study the microstructure of the material. Cu-BTC was demonstrated not only to have high CO2 adsorption capacity but also good selectivity of CO2 over N2 by means of packed bed tests. The adsorption capacity of Cu-BTC for CO2 was about 69 mL/g at 22 degrees C. The influence of the main flue gas components on the CO2 capacity of the material were discussed as well.

Interactions between Callous Unemotional Behaviors and Executive Function in Early Childhood Predict later Aggression and Lower Peer-liking in Late-childhood.

PubMed

Waller, Rebecca; Hyde, Luke W; Baskin-Sommers, Arielle R; Olson, Sheryl L

2017-04-01

Callous unemotional (CU) behaviors are linked to aggression, behavior problems, and difficulties in peer relationships in children and adolescents. However, few studies have examined whether early childhood CU behaviors predict aggression or peer-rejection during late-childhood or potential moderation of this relationship by executive function. The current study examined whether the interaction of CU behaviors and executive function in early childhood predicted different forms of aggression in late-childhood, including proactive, reactive, and relational aggression, as well as how much children were liked by their peers. Data from cross-informant reports and multiple observational tasks were collected from a high-risk sample (N = 240; female = 118) at ages 3 and 10 years old. Parent reports of CU behaviors at age 3 predicted teacher reports of reactive, proactive, and relational aggression, as well as lower peer-liking at age 10. Moderation analysis showed that specifically at high levels of CU behaviors and low levels of observed executive function, children were reported by teachers as showing greater reactive and proactive aggression, and were less-liked by peers. Findings demonstrate that early childhood CU behaviors and executive function have unique main and interactive effects on both later aggression and lower peer-liking even when taking into account stability in behavior problems over time. By elucidating how CU behaviors and deficits in executive function potentiate each other during early childhood, we can better characterize the emergence of severe and persistent behavior and interpersonal difficulties across development.

Functional Performances of CuZnAl Shape Memory Alloy Open-Cell Foams

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Electron affinities and ionization energies of Cu and Ag delafossite compounds: A hybrid functional study

NASA Astrophysics Data System (ADS)

Miao, Mao-Sheng; Yarbro, Sam; Barton, Phillip T.; Seshadri, Ram

2014-01-01

Using density functional theory with a hybrid functional, we calculate the ionization energies and electron affinities of a series of delafossite compounds (AMO2: A =Cu, Ag; M =B, Al, Ga, In, Sc). The alignments of the valence band maximum and the conduction band minimum, which directly relate to the ionization energies and electron affinities, were obtained by calculations of supercell slab models constructed in a nonpolar orientation. Our calculations reveal that the ionization energy decreases with an increasing atomic number of group-III elements, and thus suggest an improved p-type doping propensity for heavier compounds. For keeping both a low ionization energy and a band gap of sufficient size, CuScO2 is superior to the Cu-based group-III delafossites. By analyzing the electronic structures, we demonstrate that the compositional trend of the ionization energies and electron affinities is the result of a combined effect of d-band broadening due to Cu(Ag)-Cu(Ag) coupling and a repositioning of the d-band center.

CELLULAR MULTITASKING: THE DUAL ROLE OF HUMAN CU-ATPASES IN COFACTOR DELIVERY AND INTRACELLULAR COPPER BALANCE

PubMed Central

Lutsenko, Svetlana; Gupta, Arnab; Burkhead, Jason L.; Zuzel, Vesna

2008-01-01

Summary The human copper-transporting ATPases (Cu-ATPases) are essential for dietary copper uptake, normal development and function of the CNS, and regulation of copper homeostasis in the body. In a cell, Cu-ATPases maintain the intracellular concentration of copper by transporting copper into intracellular exocytic vesicles. In addition, these P-type ATPases mediate delivery of copper to copper-dependent enzymes in the secretory pathway and in specialized cell compartments such as secretory granules or melanosomes. The multiple functions of human Cu-ATPase necessitate complex regulation of these transporters that is mediated through the presence of regulatory domains in their structure, posttranslational modification and intracellular trafficking, as well as interactions with the copper chaperone Atox1 and other regulatory molecules. In this review, we summarize the current information on the function and regulatory mechanisms acting on human Cu-ATPases ATP7A and ATP7B. Brief comparison with the Cu-ATPase orthologues from other species is included. PMID:18534184

Preparation of Advanced CuO Nanowires/Functionalized Graphene Composite Anode Material for Lithium Ion Batteries

PubMed Central

Zhang, Jin; Wang, Beibei; Zhou, Jiachen; Xia, Ruoyu; Chu, Yingli; Huang, Jia

2017-01-01

The copper oxide (CuO) nanowires/functionalized graphene (f-graphene) composite material was successfully composed by a one-pot synthesis method. The f-graphene synthesized through the Birch reduction chemistry method was modified with functional group “–(CH2)5COOH”, and the CuO nanowires (NWs) were well dispersed in the f-graphene sheets. When used as anode materials in lithium-ion batteries, the composite exhibited good cyclic stability and decent specific capacity of 677 mA·h·g−1 after 50 cycles. CuO NWs can enhance the lithium-ion storage of the composites while the f-graphene effectively resists the volume expansion of the CuO NWs during the galvanostatic charge/discharge cyclic process, and provide a conductive paths for charge transportation. The good electrochemical performance of the synthesized CuO/f-graphene composite suggests great potential of the composite materials for lithium-ion batteries anodes. PMID:28772432

Analyte detection with Cu-BTC metal-organic framework thin films by means of mass-sensitive and work-function-based readout.

PubMed

Davydovskaya, Polina; Ranft, Annekatrin; Lotsch, Bettina V; Pohle, Roland

2014-07-15

Metal-organic frameworks (MOFs) constitute a new generation of porous crystalline materials, which have recently come into focus as analyte-specific active elements in thin-film sensor devices. Cu-BTC--also known as HKUST-1--is one of the most theoretically and experimentally investigated members of the MOF family. Its capability to selectively adsorb different gas molecules renders this material a promising candidate for applications in chemical gas and vapor sensing. Here, we explore details of the host-guest interactions between HKUST-1 and various analytes under different environmental conditions and study the vapor adsorption mechanism by mass-sensitive and work-function-based readouts. These complementary transduction mechanisms were successfully applied for the detection of low ppm (2 to 50 ppm) concentrations of different alcohols (methanol, ethanol, 1-propanol, and 2-propanol) adsorbed into Cu-BTC thin films. Evaluation of the results allows for the comparison of the amounts of adsorbed vapors and the contribution of each vapor to the changes of the electronic properties of Cu-BTC. The influence of the length of the alcohol chain (C1-C3) and geometry (1-propanol, 2-propanol) as well as their polarity on the sensing performance was investigated, revealing that in dry air, short chain alcohols are more likely adsorbed than long chain alcohols, whereas in humid air, this preference is changed, and the sensitivity toward alcohols is generally decreased. The adsorption mechanism is revealed to differ for dry and humid atmospheres, changing from a site-specific binding of alcohols to the open metal sites under dry conditions to weak physisorption of the analytes dissolved in surface-adsorbed water reservoirs in humid air, with the signal strength being governed by their relative concentration.

Fabrication of selectively functionalized-graphene reinforced copper phthalocyanine nanocomposites with low dielectric loss and high dielectric constant

NASA Astrophysics Data System (ADS)

Wang, Zicheng; Wei, Renbo; Liu, Xiaobo

2017-01-01

A novel kind of selectively functionalized-graphene reinforced copper phthalocyanine (RGO-O-CuPc) nanocomposites was successfully fabricated through a facile and effective three-step method, involving preferential surficial modification and reduction of graphene oxide (GO) sheets, and followed by incorporating with CuPc via in situ polymerization. The results of SEM, AFM, XPS, FTIR, XRD and UV-vis confirmed that GO was effectively surficial functionalized by a ring-open covalent reaction between amino in 3-aminophenoxyphthalonitrile (3-APN) and epoxy groups on the GO sheets, and partly reduced back to graphene under solvothermal conditions. And the RGO-O-CuPc was successfully fabricated by self-assembling of CuPc molecule on graphene sheets via in situ polymerization. As a consequence, the selective surface functionalization and solvothermal reduction of GO facilitated the improvement in the dielectric constant and AC conductivity, and the decrease in the dielectric loss of the graphene/CuPc nanocomposites.

10.3%-efficient submicron-thick Cu(In,Ga)Se2 solar cells with absorber fabricated by sputtering In2Se3, CuGaSe2 and Cu2Se targets

NASA Astrophysics Data System (ADS)

Peng, Xiao; Zhao, Ming; Zhuang, Daming; Sun, Rujun; Zhang, Leng; Wei, Yaowei; Lv, Xunyan; Wu, Yixuan; Ren, Guoan

2018-06-01

We reported a new method to fabricate submicron-thick CIGS with smooth surface by sputtering In2Se3, CuGaSe2 and Cu2Se targets with post-selenization. The influence of gallium content on the properties of CIGS thin film was evaluated by the crystallinity and the cells performance. The most suitable value of Ga content in our submicron-thick CIGS is 0.32 and cells based on it demonstrated the highest efficiency of 10.3%.

Influence of heavy metals on the formation and the distribution behavior of PAH and PCDD/F during simulated fires.

PubMed

Wobst, M; Wichmann, H; Bahadir, M

2003-04-01

Combustion experiments were performed with an artificial fire load (polystyrene and quartz powder) in a laboratory scale incinerator in the presence of gaseous HCl to simulate accidental fire conditions. The aim of this investigation was to trace back the alterations of the formation and the distribution behavior of PAH and PCDD/PCDF to the presence of CuO or a mixture of metal oxides (CdO, CuO, Fe(2)O(3), PbO, MoO(3), ZnO). The total amount of the 16 PAH target compounds was reduced by the factor of 5-9 when the mixture of metal oxides was present rather than merely CuO. PAH patterns as well as their distribution behavior were significantly influenced by these oxides. In general, transportation inside the installation was enhanced for most of the 16 analyzed PAH. Only fluorene and dibenzo[a,h]anthracene were transported to a smaller extent. In contrast to PAH, total concentrations of PCDD were increased by factor 9 and of PCDF by factor 10, respectively, when CuO was present. Adding the mixture of metal oxides resulted in an increase of PCDD by factor 14 and of PCDF by factor 7. CuO and the mixture of metal oxides had a different influence on the PCDD/F homologue patterns. For instance, the HxCDF to OCDF ratio after incineration without any metal oxide was 1 to 6, whereas addition of CuO or the mixture of the metal oxides shifted the HxCDF to OCDF ratios towards 1 to 40 or 1 to 17, respectively. Combustion along with CuO increased transportation of higher chlorinated PCDF congeners, whereas the mixture of the metal oxides caused a strong decrease of PCDF distribution throughout the system.

Fate of copper complexes in hydrothermally altered deep-sea sediments from the Central Indian Ocean Basin.

PubMed

Chakraborty, Parthasarathi; Sander, Sylvia G; Jayachandran, Saranya; Nath, B Nagender; Nagaraju, G; Chennuri, Kartheek; Vudamala, Krushna; Lathika, N; Mascarenhas-Pereira, Maria Brenda L

2014-11-01

The current study aims to understand the speciation and fate of Cu complexes in hydrothermally altered sediments from the Central Indian Ocean Basin and assess the probable impacts of deep-sea mining on speciation of Cu complexes and assess the Cu flux from this sediment to the water column in this area. This study suggests that most of the Cu was strongly associated with different binding sites in Fe-oxide phases of the hydrothermally altered sediments with stabilities higher than that of Cu-EDTA complexes. The speciation of Cu indicates that hydrothermally influenced deep-sea sediments from Central Indian Ocean Basin may not significantly contribute to the global Cu flux. However, increasing lability of Cu-sediment complexes with increasing depth of sediment may increase bioavailability and Cu flux to the global ocean during deep-sea mining. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electronic Structure of the [Cu 3 (μ-O) 3] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

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

Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J. M.

Identifying Cu-exchanged zeolites able to activate C–H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu 3(μ-O) 3] 2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu 3(μ-O) 3] 2+ site using multiconfigurational wave-function-based methods and densitymore » functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C–H activation of methane by [Cu 3(μ-O) 3] 2+. These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.« less

Electronic Structure of the [Cu 3 (μ-O) 3] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

DOE PAGES

Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J. M.; ...

2017-09-28

Identifying Cu-exchanged zeolites able to activate C–H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu 3(μ-O) 3] 2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu 3(μ-O) 3] 2+ site using multiconfigurational wave-function-based methods and densitymore » functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C–H activation of methane by [Cu 3(μ-O) 3] 2+. These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.« less

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

Rudeck, P.J.; Harper, J.M.E.; Fryer, P.M.

The copper concentration in aluminum--copper alloys can be altered by ion bombardment during film deposition. We have measured the sputtering yields of aluminum and copper in Al--Cu alloys as a function of the Cu concentration (5--13 at. %) and the angle of ion incidence (0--40/sup 0/ from normal). During deposition, the films were partially resputtered by 500-eV Ar/sup +/ ion bombardment from a Kaufman ion source. We found that the Cu sputtering yield decreases by up to a factor of 10 in the alloy, relative to elemental Cu. The Al sputtering yield remains close to the elemental value. The netmore » effect is a strong preferential sputtering of Al relative to Cu, which enhances the Cu concentration in an ion bombarded film. The Al/Cu sputtering yield ratio for normal incidence ion bombardment ranges from 3 to 5 as a function of Cu concentration. This ratio decreases with increasing angle of incidence to as low as 2 for 40/sup 0/ incident ions. However, since a higher fraction of the film is resputtered from a sloping surface, a higher Cu concentration is found on a sloping surface relative to a flat surface. These results show that in multicomponent film deposition under ion bombardment, the film composition will vary as a function of the surface topography. We will also show how the level of argon left trapped in the films varies inversely with respect to the ion flux.« less

Combinational effects of sulfomethoxazole and copper on soil microbial community and function.

PubMed

Liu, Aiju; Cao, Huansheng; Yang, Yan; Ma, Xiaoxuan; Liu, Xiao

2016-03-01

Sulfonamides and Cu are largely used feed additives in poultry farm. Subsequently, they are spread onto agricultural soils together with contaminated manure used as fertilizer. Both sulfonamides and Cu affect the soil microbial community. However, an interactive effect of sulfonamides and Cu on soil microorganisms is not well understood. Therefore, a short-time microcosm experiment was conducted to investigate the interaction of veterinary antibiotic sulfomethoxazole (SMX) and Cu on soil microbial structure composition and functions. To this end, selected concentrations of SMX (0, 5, and 50 mg kg(-1)) and Cu (0, 300, and 500 mg kg(-1)) were combined, respectively. Clear dose-dependent effects of SMX on microbial biomass and basal respiration were determined, and these effects were amplified in the presence of additional Cu. For activities of soil enzymes including β-glucosidase, urease, and protease, clear reducing effects were determined in soil samples containing 5 or 50 mg kg(-1) of SMX, and the interaction of SMX and Cu was significant, particularly in soil samples containing 50 mg kg(-1) SMX or 500 mg kg(-1) Cu. SMX amendments, particularly in combination with Cu, significantly reduced amounts of the total, bacterial, and fungal phospholipid fatty acids (PLFAs) in soil. Moreover, the derived ratio of bacteria to fungi decreased significantly with incremental SMX and Cu, and principal component analysis of the PLFAs showed that soil microbial composition was significantly affected by SMX interacted with Cu at 500 mg kg(-1). All of these results indicated that the interaction of SMX and Cu was synergistic to amplify the negative effect of SMX on soil microbial biomass, structural composition, and even the enzymatic function.

Influence of post-deposition annealing on structural, morphological and optical properties of copper (II) acetylacetonate thin films.

PubMed

Abdel-Khalek, H; El-Samahi, M I; El-Mahalawy, Ahmed M

2018-05-21

In this study, the effect of thermal annealing under vacuum conditions on structural, morphological and optical properties of thermally evaporated copper (II) acetylacetonate, cu(acac) 2 , thin films were investigated. The copper (II) acetylacetonate thin films were deposited using thermal evaporation technique at vacuum pressure ~1 × 10 -5  mbar. The deposited films were thermally annealed at 323, 373, 423, and 473 K for 2 h in vacuum. The thermogravimetric analysis of cu(acac) 2 powder indicated a thermal stability of cu(acac) 2 up to 423 K. The effects of thermal annealing on the structural properties of cu(acac) 2 were evaluated employing X-ray diffraction method and the analysis showed a polycrystalline nature of the as-deposited and annealed films with a preferred orientation in [1¯01] direction. Fourier transformation infrared (FTIR) technique was used to negate the decomposition of copper (II) acetylacetonate during preparation or/and annealing up to 423 K. The surface morphology of the prepared films was characterized by means of field emission scanning electron microscopy (FESEM). A significant enhancement of the morphological properties of cu(acac) 2 thin films was obtained till the annealing temperature reaches 423 K. The variation of optical constants that estimated from spectrophotometric measurements of the prepared thin films was investigated as a function of annealing temperature. The annealing process presented significantly impacted the nonlinear optical properties such as third-order optical susceptibility χ (3) and nonlinear refractive index n 2 of cu(acac) 2 thin films. Copyright © 2018 Elsevier B.V. All rights reserved.

Ethnic studies of dietary intakes of zinc, copper, iron, and calcium

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

Matthews, C.; Figueroa, M.; Tam, C.F.

1986-01-01

Immigrants, such as S.E. Asians who live in the L.A. area, often suffer high incidences of diseases. It is of interest to examine ethnic eating patterns whether they influence dietary Zn, Cu, Fe, Ca, protein and Kcal, which are essential for proper immune functions. Three-day dietary intake of adult ethnic groups, Asian(A)(N=18), Caucasian(C)(26), Black(B)(7), Latino(L)(12), Middle Easterner(ME)(9) and Filipino(F)(6) were analyzed for Zn, Cu, Fe, Ca, protein and Kcal by Ohio Data Base Foods II(ODBF) then statistically compared by PROPHET. Zn and Cu were also analyzed by hand calculation(HC). No statistical differences were observed for mean Zn between groups analyzedmore » by ODBF whereas HC of mean Zn between A vs C (A=11.3 +/- S.D.2.9 mg vs C=8.8 +/- 2.8, P<0.01) and A vs L (11.3+/-2.9 vs L=8.9+/-2.2, P<0.05) were statistically different. No differences were found for Cu between the groups. By ODBF, none of mean Cu or Zn met 2/3 RDA for any of the groups. For Fe, no differences were found between groups and only 50% of the subjects met 2/3 RDA. Significant differences were observed for Ca only between A vs C and B vs C. Both A and B had lower mean Ca than C. All groups had adequate protein. Mean Kcal of all groups were found to be at or about 2/3 RDA. Both insufficient Kcal and eating patterns contribute to inadequate Cu, Zn, and Fe intakes and hence may affect immune competency.« less

Mononuclear Cu/O2 Complexes

PubMed Central

Cramer, Christopher J.; Tolman, William B.

2008-01-01

Using interwoven experimental and theoretical methods, detailed studies of several structurally defined 1:1 Cu/O2 complexes have provided important fundamental chemical information useful for understanding the nature of intermediates involved in aerobic oxidations in synthetic and enzymatic copper-mediated catalysis. In particular, these studies have shed new light onto the factors that influence the mode of O2 coordination (end-on vs. side-on) and the electronic structure, which can vary between Cu(II)-superoxo and Cu(III)-peroxo extremes. PMID:17458929

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

Zhukov, A. A., E-mail: azhukov@issp.ac.ru; Chernysheva, M. V.; Eliseev, A. A.

We report the results on the measurements of the work function of single-walled carbon nanotubes encapsulated by Agl (AgI@SWCNT), AgCl (AgCl@SWCNT), and CuBr (CuBr@SWCNT) by the local Kelvin probe technique. We found the values of the work function of tubes encapsulated with AgI and AgCl (Φ(AgI@SWCNT) = 5.08 ± 0.02, Φ(AgCl@SWCNT) = 5.10 ± 0.02 eV) to exceed substantially that of pristine carbon nanotubes, and the value of the work function of carbon nanotubes encapsulated with CuBr is Φ(CuBr@SWCNT) = 4.89 ± 0.03 (eV). The measurements are carried out using different kinds of microscope probes including multi-walled carbon nanotube tips.

Etude de l'electrocatalyse de la reduction de l'oxygene sur des alliages de palladium cuivre

NASA Astrophysics Data System (ADS)

Fouda-Onana, Frederic

This thesis is on the development of the ORR on Pd-Cu alloys in acid medium. Density Functional Theory (DFT) was used to determine the intrinsic properties of the alloys. The alloys were fabricated by RF sputtering on glassy carbon support and chemical salt reduction on carbon support. They characterised by electrochemical methods and correlations were made between the intrinsic properties and the experimental electrochemical parameters. These correlations were used to explain the electrocatalytic performance of the ORR on these aklooys and to determine the mechanism of this reaction on these electrocatalysts. Accordingly the following aspects were studied in details. In the first step, ab initio investigations of the effect of the intermediate adsorption on the variation of the reversible potential of the ORR on Pt(100) was shown. Density Functional Theory (DFT) was used to determine the energies and the geometry parameters of the intermediates which can be adsorbed on Pt(100) during the oxygen reduction reaction (ORR) and their effect on the . The Comparison of these energies and parameters using the Bridge or the Griffiths sites adsorption mechanism suggests that the two paths are feasible. In both mechanisms, the total adsorption energies of the intermediates species continuously decrease. Moreover, according to the geometry analysis, the O-O bond distance in H2O2 is higher in both (Bridge and Griffiths) processes compared to the gas phase. Such a result suggests a dissociative H2O2 adsorption whatever the type of the involved mechanism involved. In the second step, the Oxygen reduction reaction (ORR) on palladium-copper alloys was studied through two approaches. The first one is based on the correlations between the surface chemical composition and the kinetics parameters of the ORR. The second approach is focused on the correlations between the adsorption energies of O2 and OH of Pd-Cu(111) surfaces and the electronic properties of the alloys. The adsorbtion energy calculations are based on on ab initio calculation using the program VASP (Vienna ab initio program) in a MeDeA environnement (software purchased from Materials Design, Inc. The studies of the oxygen reduction reaction were performed in an acidic media on Palladium-Copper alloys as catalyst. The variation of the intrinsic metal surface properties (lattice parameter, binding energy, work function (Wf), d-band filling and d-band center epsilond) and O2 and OH adsorption energies of on (111) Pd-Cu surface alloys were determined using ab initio program. Calculations of these parameters were based on plane waves approach on slab system with density functional theory (DFT) using the Vienna ab initio simulation program (VASP). It was shown that insertion of Cu atoms in Pd lattice affects geometric and electronic properties of Pd. These changes influence significantly O2 and OH adsorption. In the third step, the oxygen reduction reaction (ORR) on Pd-Cu catalyst has been studied in acidic media. The palladium alloys were prepared by RF magnetron using a palladium and a copper wafer as targets on the glassy carbon substrate. The dual sputtering we used allowed the deposition of about 1micrometer thin film of Pd-Cu on glassy carbon (GC). The ORR kinetics was studied on these catalysts in 0,1M HClO4. Cyclic voltammetry (CV) was used to determine the electrochemical active surface area (Sa). An increase in Sa with the Cu content in the alloy was observed for the alloys containing more than 50% in Cu. The Pd-Cu alloys containing more than 50% in Cu exhibits a constant value of 23 cm2 for Sa. It was further shown that the ORR on the Pd-Cu alloys proceeds through the 4 electrons transfer mechanism and a Tafel slope of 60 mV/dec. The Pd 50Cu50 exhibits the highest activity for this reaction. The enhancement of the electro catalytic activity is attributed to an optimal d band property that makes easier the OOH dissociative adsorption which is considered as chemical rate determining step (RDS) for the ORR. It was also found that all the Pd-Cu alloys exhibited better electrocatalystic performances for the ORR than Pd or Cu alone. From the polarisation of the ORR in 0,1 M HClO4 it was shown that the curve of the Pd electrode was shifted to the lower potentials than those of the Pd-Cu alooys. In addition, the variation of the kinetic current of the ORR at 0,6 V vs. SCE (0,841 V vs. RHE) on the Pd-Cu alloys with the composition of in Cu content exhibited a volcano-shape. (Abstract shortened by UMI.)

Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

PubMed

Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

2007-03-01

Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1.

Morphological and functional responses of a metal-tolerant sunflower mutant line to a copper-contaminated soil series.

PubMed

Kolbas, Aliaksandr; Kolbas, Natallia; Marchand, Lilian; Herzig, Rolf; Mench, Michel

2018-04-02

The potential use of a metal-tolerant sunflower mutant line for biomonitoring Cu phytoavailability, Cu-induced soil phytotoxicity, and Cu phytoextraction was assessed on a Cu-contaminated soil series (13-1020 mg Cu kg -1 ) obtained by fading a sandy topsoil from a wood preservation site with a similar uncontaminated soil. Morphological and functional plant responses as well as shoot, leaf, and root ionomes were measured after a 1-month pot experiment. Hypocotyl length, shoot and root dry weight (DW) yields, and leaf area gradually decreased as soil Cu exposure rose. Their dose-response curves (DRC) plotted against indicators of Cu exposure were generally well fitted by sigmoidal curves. The half-maximal effective concentration (EC 50 ) of morphological parameters ranged between 203 and 333 mg Cu kg -1 soil, corresponding to 290-430 μg Cu L -1 in the soil pore water, and 20 ± 5 mg Cu kg -1 DW in the shoots. The EC 10 for shoot Cu concentration (13-15 mg Cu kg -1 DW) coincided to 166 mg Cu kg -1 soil. Total chlorophyll content and total antioxidant capacity (TAC) were early biomarkers (EC 10 : 23 and 51 mg Cu kg -1 soil). Their DRC displayed a biphasic response. Photosynthetic pigment contents, e.g., carotenoids, correlated with TAC. Ionome was changed in Cu-stressed roots, shoots, and leaves. Shoot Cu removal peaked roughly at 280 μg Cu L -1 in the soil pore water.

Atomistic models of Cu diffusion in CuInSe2 under variations in composition

NASA Astrophysics Data System (ADS)

Sommer, David E.; Dunham, Scott T.

2018-03-01

We construct an analytic model for the composition dependence of the vacancy-mediated Cu diffusion coefficient in undoped CuInSe2 using parameters from density functional theory. The applicability of this model is supported numerically with kinetic lattice Monte Carlo and Onsager transport tensors. We discuss how this model relates to experimental measurements of Cu diffusion, arguing that our results can account for significant contributions to the bulk diffusion of Cu tracers in non-stoichiometric CuInSe2.

Overexpression of amyloid precursor protein increases copper content in HEK293 cells

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

Suazo, Miriam; Hodar, Christian; Morgan, Carlos

2009-05-15

Amyloid precursor protein (APP) is a transmembrane glycoprotein widely expressed in mammalian tissues and plays a central role in Alzheimer's disease. However, its physiological function remains elusive. Cu{sup 2+} binding and reduction activities have been described in the extracellular APP135-156 region, which might be relevant for cellular copper uptake and homeostasis. Here, we assessed Cu{sup 2+} reduction and {sup 64}Cu uptake in two human HEK293 cell lines overexpressing APP. Our results indicate that Cu{sup 2+} reduction increased and cells accumulated larger levels of copper, maintaining cell viability at supra-physiological levels of Cu{sup 2+} ions. Moreover, wild-type cells exposed to bothmore » Cu{sup 2+} ions and APP135-155 synthetic peptides increased copper reduction and uptake. Complementation of function studies in human APP751 transformed Fre1 defective Saccharomyces cerevisiae cells rescued low Cu{sup 2+} reductase activity and increased {sup 64}Cu uptake. We conclude that Cu{sup 2+} reduction activity of APP facilitates copper uptake and may represent an early step in cellular copper homeostasis.« less

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Influence of salicylic acid pretreatment on seeds germination and some defence mechanisms of Zea mays plants under copper stress.

PubMed

Moravcová, Šárka; Tůma, Jiří; Dučaiová, Zuzana Kovalíková; Waligórski, Piotr; Kula, Monika; Saja, Diana; Słomka, Aneta; Bąba, Wojciech; Libik-Konieczny, Marta

2018-01-01

The study was focused on the influence of salicylic acid (SA) on maize seeds germination and on some physiological and biochemical processes in maize plants growing in the hydroponic culture under copper (Cu) stress. A significant influence of SA pretreatment on the advanced induction of the maize seeds metabolic activity and the level of the endogenous SA in germinated seeds and developing roots have been stated. Although, the ability of maize seeds to uptake SA and accumulate it in the germinated roots was confirmed, the growth inhibition of Cu-stressed maize seedlings was not ameliorated by SA seeds pretreatment. Cu-stressed plants exhibited a decrease in the photosynthetic pigment concentration and the increase in non-photochemical quenching (NPQ) - an indicator of an excess energy in PSII antenna assemblies lost as a heat. The amelioration effect of SA application was found only for carotenoids content which increased in stressed plants. It was also shown that maize roots growing in stress conditions significantly differed in the chemical composition in comparison to the roots of control plants, but the SA pretreatment did not affect these differences. On the other hand, it was found that SA seed pretreatment significantly influenced the ability of stressed plants to accumulate copper in the roots. It was stated that a higher level of exogenous SA application led to a lower accumulation of Cu ions in maize roots. Cu-stressed plants exhibited higher oxidative stress in roots than in leaves which was manifested as an increase in the concentration of hydrogen peroxide due to stress factor application. We observed an increase in catalase (CAT) activity in leaves of Cu-stressed plants which corresponded with a lower H 2 O 2 content when compared with roots where the hydrogen peroxide level was higher, and the inhibition of the CAT activity was found. Furthermore, we found that the SA seed pretreatment led to a decrease in the H 2 O 2 content in the roots of the Cu-stressed plants, but it did not influence the H 2 O 2 level in leaves. The increase in hydrogen peroxide content in the roots of Cu-stressed plants correlated with a higher activity of the MnSODI and MnSODII isoforms. It was found that SA pretreatment caused a decrease in MnSODII activity accompanied by the decrease in H 2 O 2 concentration. Achieved results indicated also that the changes in the chemical composition of the root tissue under copper stress constituted protection mechanisms of blocking copper flow into other plant organs. However, it might be assumed that the root tissue remodelling under Cu stress did not only prevent against the Cu ions uptake but also limited the absorption of minerals required for the normal growth leading to the inhibition of the plant development. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Effects of copper particles on a model septic system's function and microbial community.

PubMed

Taylor, Alicia A; Walker, Sharon L

2016-03-15

There is concern surrounding the addition of nanoparticles into consumer products due to toxicity potential and the increased risk of human and environmental exposures to these particles. Copper nanoparticles are found in many common consumer goods; therefore, the disposal and subsequent interactions between potentially toxic Cu-based nanoparticles and microbial communities may have detrimental impacts on wastewater treatment processes. This study investigates the effects of three copper particles (micron- and nano-scale Cu particles, and a nano-scale Cu(OH)2-based fungicide) on the function and operation of a model septic tank. Septic system analyses included water quality evaluations and microbial community characterizations to detect changes in and relationships between the septic tank function and microbial community phenotype/genotype. As would be expected for optimal wastewater treatment, biological oxygen demand (BOD5) was reduced by at least 63% during nano-scale Cu exposure, indicating normal function. pH was reduced to below the optimum anaerobic fermentation range during the micro Cu exposure, suggesting incomplete degradation of organic waste may have occurred. The copper fungicide, Cu(OH)2, caused a 57% increase in total organic carbon (TOC), which is well above the typical range for septic systems and also corresponded to increased BOD5 during the majority of the Cu(OH)2 exposure. The changes in TOC and BOD5 demonstrate that the system was improperly treating waste. Overall, results imply individual exposures to the three Cu particles caused distinct disruptions in septic tank function. However, it was observed that the system was able to recover to typical operating conditions after three weeks post-exposure. These results imply that during periods of Cu introduction, there are likely pulses of improper removal of total organic carbon and significant changes in pH not in the optimal range for the system. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rapid synthesis of Fe-doped CuO-Ce0.8Zr0.2O2 catalysts for CO preferential oxidation in H2-rich streams: Effect of iron source and the ratio of Fe/Cu

NASA Astrophysics Data System (ADS)

Wang, Jing; Han, Caiyun; Gao, Xiaoya; Lu, Jichang; Wan, Gengpin; He, Dedong; Chen, Ran; Chen, Kezhen; He, Sufang; Luo, Yongming

2017-03-01

A facile route (urea grind combustion method) is described for the rapid synthesis of Fe-doped Cu-Ce-Zr catalysts within 30 min through simple grinding and combustion. The effects of iron source and Fe/Cu mass ratio on the performances of the catalysts for CO preferential oxidation (CO-PROX) are evaluated. The influences of H2O, CO2, and their mixture on the activity as well as stability of the catalysts are also investigated. The samples are characterized by XRD, N2 adsorption-desorption, H2-TPR, TEM, Raman and XPS. Fe(NO3)3 is found to be superior to FeCl3 and Fe2(SO4)3 as the iron source for Fe-CuCZ catalyst. Among the different synthesized catalysts, 1/10Fe(N)-CuCZ is found to be the most active catalyst, indicating that the optimal Fe/Cu mass ratio is 1/10. The influences of H2O, CO2, and H2O + CO2 on the catalytic performance of 1/10Fe(N)-CuCZ are in the order of CO2 < CO2 + H2O < H2O. 1/10Fe(N)-CuCZ exhibits excellent stability during a 228 h time-on-stream test. 1/10Fe(N)-CuCZ shows the highest catalytic activity and excellent stability even in the presence of H2O and CO2. The excellent catalytic performance can be attributed to the synergy between the highly dispersed copper species and ceria, as well as the formation of more oxygen vacancies and reduced copper species.

Influence of La addition on the semi-conductive properties of passive films formed on Cu-Ni alloy

NASA Astrophysics Data System (ADS)

Leng, Xiang; Zhang, Yadong; Zhou, Qiongyu; Zhang, Yinghui; Wang, Zhigang; Wang, Hang; Yang, Bin

2018-05-01

The semi-conductive properties of passive films formed on Cu-Ni alloy and Cu-Ni-La alloy were investigated in 0.1 M NaOH solution, by employing electrochemical impedance spectroscopy (EIS), Mott–Schottky analysis and point defect model (PDM). Results indicate that both the passive films formed on Cu-Ni alloy and Cu-Ni-La alloy display p-type semi-conductive characteristics with cation vacancies in order of magnitude of 1020 cm3. Compared with Cu-Ni alloy, La addition could significantly improve the corrosion resistance, due to a superior barrier passive film formed Cu-Ni-La alloy with a bigger film resistance (R f), increased passive film thickness (L ss) in conjunction with decreased diffusion coefficient (D 0).

Influence of Cu on modifying the beta phase and enhancing the mechanical properties of recycled Al-Si-Fe cast alloys.

PubMed

Basak, C B; Babu, N Hari

2017-07-18

High iron impurity affects the castability and the tensile properties of the recycled Al-Si alloys due to the presence of the Fe containing intermetallic β-Al 9 Fe 2 Si 2 phase. To date only Mn addition is known to transform the β-Al 9 Fe 2 Si 2 phase in the Al-Si-Fe system. However, for the first time, as reported here, it is shown that β-phase transforms to the ω-Al 7 Cu 2 Fe phase in the presence of Cu, after solutionization at 793 K. The ω-phase decomposes below 673 K resulting into the formation of θ-Al 2 Cu phase. However, the present thermodynamic description of the Al-Si-Fe-Cu system needs finer tuning to accurately predict the stability of the ω-phase in these alloys. In the present study, an attempt was made to enhance the strength of Al-6wt%Si-2wt%Fe model recycled cast alloy with different amount of Cu addition. Microstructural and XRD analysis were carried out in detail to show the influence of Cu and the stability range of the ω-phase. Tensile properties and micro-hardness values are also reported for both as-cast and solutionized alloys with different amount of Cu without and with ageing treatment at 473 K. The increase in strength due to addition of Cu, in Fe-rich Al-Si alloys is promising from the alloy recyclability point of view.

Macroscopic and molecular approaches of enrofloxacin retention in soils in presence of Cu(II).

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2013-10-15

The co-adsorption of copper and the fluoroquinolone antibiotic enrofloxacin (ENR) at the water-soil interface was studied by means of batch adsorption experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The system was investigated over a pH range between 6 and 10, at different contact times, ionic strengths, and ENR concentrations. Adsorption coefficient - Kd - was determined at relevant environmental concentrations and the value obtained in water at a ionic strength imposed by the soil and at soil natural pH was equal to 0.66Lg(-1). ENR adsorption onto the soil showed strong pH dependence illustrating the influence of the electrostatic interactions in the sorption processes. The simultaneous co-adsorption of ENR and Cu(II) on the soil was also investigated. The presence of Cu(II) strongly influenced the retention of the antibiotic, leading to an increase up to 35% of adsorbed ENR amount. The combined quantitative and spectroscopic results showed that Cu(II) and ENR directly interacted at the water-soil interface to form ternary surface complexes. Cu K-edge EXAFS data indicated a molecular structure where the carboxylate and carbonyl groups of ENR coordinate to Cu(II) to form a 6-membered chelate ring and where Cu(II) bridges between ENR and the soil surface sites. Cu(II) bonds bidentately to the surface in an inner-sphere mode. Thus, the spectroscopic data allowed us to propose the formation of ternary surface complexes with the molecular architecture soil-Cu(II)-ENR. Copyright © 2013 Elsevier Inc. All rights reserved.

Numerical analysis and optimization of Cu2O/TiO2, CuO/TiO2, heterojunction solar cells using SCAPS

NASA Astrophysics Data System (ADS)

Sawicka-Chudy, Paulina; Sibiński, Maciej; Wisz, Grzegorz; Rybak-Wilusz, Elżbieta; Cholewa, Marian

2018-05-01

In the presented work, the Cu2O/TiO2 and CuO/TiO2 heterojunction solar cells have been analyzed by the help of Solar Cell Capacitance Simulator (SCAPS). The effects of various layer parameters like thickness and defect density on the cell performance have been studied in details. Numerical analysis showed how the absorber (CuO, Cu2O) and buffer (TiO2) layers thickness influence the short-circuit current density (Jsc) and efficiency (η) of solar cells. Optimized solar cell structures of Cu2O/TiO2 and CuO/TiO2 showed a potential efficiency of ∼9 and ∼23%, respectively, under the AM1.5G spectrum. Additionally, external quantum efficiency (EQE) curves of the CuO/TiO2 and Cu2O/TiO2 solar cells for various layers thickness of TiO2 were calculated and the optical band gap (Eg) for CuO and Cu2O was obtained. Finally, we examined the effects of defect density on the photovoltaic parameters.

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

PubMed

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

2016-10-01

Copper-zinc-superoxide dismutase (CuZnSOD) from Hippocampus abdominalis (HaCuZnSOD) is a metalloenzyme which belongs to the ubiquitous family of SODs. Here, we determined the characteristic structural features of HaCuZnSOD, analyzed its evolutionary relationships, and identified its potential immune responses and biological functions in relation to antioxidant defense mechanisms in the seahorse. The gene had a 5' untranslated region (UTR) of 67 bp, a coding sequence of 465 bp and a 3' UTR of 313 bp. The putative peptide consists of 154 amino acids. HaCuZnSOD had a predicted molecular mass of 15.94 kDa and a theoretical pI value of 5.73, which is favorable for copper binding activity. In silico analysis revealed that HaCuZnSOD had a prominent Cu-Zn_superoxide_dismutase domain, two Cu/Zn signature sequences, a putative N-glycosylation site, and several active sites including Cu(2+) and Zn(2+) binding sites. The three dimensional structure indicated a β-sheet barrel with 8 β-sheets and two short α-helical regions. Multiple alignment analyses revealed many conserved regions and active sites among its orthologs. The highest amino acid identity to HaCuZnSOD was found in Siniperca chuatsi (87.4%), while Maylandia zebra shared a close relationship in the phylogenetic analysis. Functional assays were performed to assess the antioxidant, biophysical and biochemical properties of overexpressed recombinant (r) HaCuZnSOD. A xanthine/XOD assay gave optimum results at pH 9 and 25 °C indicating these may be the best conditions for its antioxidant action in the seahorse. An MTT assay and flow cytometry confirmed that rHaCuZnSOD showed peroxidase activity in the presence of HCO3(-). In all the functional assays, the level of antioxidant activity of rHaCuZnSOD was concentration dependent; metal ion supplementation also increased its activity. The highest mRNA expressional level of HaCuZnSOD was found in blood. Temporal assessment under pathological stress showed a delay response by HaCuZnSOD. Our findings demonstrated that HaCuZnSOD is an important antioxidant, which might be involved in the host antioxidant defense mechanism against oxidative stress. Copyright © 2016 Elsevier Ltd. All rights reserved.

The importance of carbon nanotube wire density, structural uniformity, and purity for fabricating homogeneous carbon nanotube-copper wire composites by copper electrodeposition

NASA Astrophysics Data System (ADS)

Sundaram, Rajyashree; Yamada, Takeo; Hata, Kenji; Sekiguchi, Atsuko

2018-04-01

We present the influence of density, structural regularity, and purity of carbon nanotube wires (CNTWs) used as Cu electrodeposition templates on fabricating homogeneous high-electrical performance CNT-Cu wires lighter than Cu. We show that low-density CNTWs (<0.6 g/cm3 for multiwall nanotube wires) with regular macro- and microstructures and high CNT content (>90 wt %) are essential for making homogeneous CNT-Cu wires. These homogeneous CNT-Cu wires show a continuous Cu matrix with evenly mixed nanotubes of high volume fractions (˜45 vol %) throughout the wire-length. Consequently, the composite wires show densities ˜5.1 g/cm3 (33% lower than Cu) and electrical conductivities ˜6.1 × 104 S/cm (>100 × CNTW conductivity). However, composite wires from templates with higher densities or structural inconsistencies are non-uniform with discontinuous Cu matrices and poor CNT/Cu mixing. These non-uniform CNT-Cu wires show conductivities 2-6 times lower than the homogeneous composite wires.

Disintegration of the net-shaped grain-boundary phase by multi-directional forging and its influence on the microstructure and properties of Cu-Ni-Si alloy

NASA Astrophysics Data System (ADS)

Zhang, Jinlong; Lu, Zhenlin; Zhao, Yuntao; Jia, Lei; Xie, Hui; Tao, Shiping

2017-09-01

Cu-Ni-Si alloys with 90% Cu content and Ni to Si ratios of 5:1 were fabricated by fusion casting, and severe plastic deformation of the Cu-Ni-Si alloy was carried out by multi-direction forging (MDF). The results showed that the as-cast and homogenized Cu-Ni-Si alloys consisted of three phases, namely the matrix phase α-Cu (Ni, Si), the reticular grain boundary phase Ni31Si12 and the precipitated phase Ni2Si. MDF significantly destroyed the net-shaped grain boundary phase, the Ni31Si12 phase and refined the grain size of the Cu matrix, and also resulted in the dissolving of Ni2Si precipitates into the Cu matrix. The effect of MDF on the conductivity of the solid solution Cu-Ni-Si alloy was very significant, with an average increase of 165.16%, and the hardness of the Cu-Ni-Si alloy also increased obviously.

Synthesis of Higher Alcohols via Syngas on Cu/Zn/Si Catalysts. Effect of Polyethylene Glycol Content

NASA Astrophysics Data System (ADS)

Cui, Rong-Ji; Yan, Xing; Fan, Jin-Chuan; Huang, Wei

2018-05-01

Cu/Zn/Si catalysts with different polyethylene glycol (PEG) content were prepared by a complete liquid-phase method, and characterized by XRD, H2-TPR, N2-adsorption, and XPS. The influence of PEG content on the higher alcohols synthesis from syngas was investigated. The results showed that addition of PEG can influence the texture and surface properties of the catalysts, and therefore affect their activity and product distribution. With an increase in PEG content, BET surface area, Cu crystallite size and surface active ingredient content of the catalysts first increased and then decreased, the CO conversion had similar variation tendency. However, the pore volume and pore diameter of the catalyst increased, and the binding energy of the active component and the content of Cu2O decreased, which resulted in higher catalyst selectivity towards higher alcohols. The highest C2+OH selectivity in total alcohols was 60.6 wt %.

Copper toxicity in Chinese cabbage is not influenced by plant sulphur status, but affects sulphur metabolism-related gene expression and the suggested regulatory metabolites.

PubMed

Shahbaz, M; Stuiver, C E E; Posthumus, F S; Parmar, S; Hawkesford, M J; De Kok, L J

2014-01-01

The toxicity of high copper (Cu) concentrations in the root environment of Chinese cabbage (Brassica pekinensis) was little influenced by the sulphur nutritional status of the plant. However, Cu toxicity removed the correlation between sulphur metabolism-related gene expression and the suggested regulatory metabolites. At high tissue Cu levels, there was no relation between sulphur metabolite levels viz. total sulphur, sulphate and water-soluble non-protein thiols, and the expression and activity of sulphate transporters and expression of APS reductase under sulphate-sufficient or-deprived conditions, in the presence or absence of H2 S. This indicated that the regulatory signal transduction pathway of sulphate transporters was overruled or by-passed upon exposure to elevated Cu concentrations. © 2013 German Botanical Society and The Royal Botanical Society of the Netherlands.

Tuning to the band gap by complex defects engineering: insights from hybrid functional calculations in CuInS2

NASA Astrophysics Data System (ADS)

Yang, Pei; Shi, Li-Jie; Zhang, Jian-Min; Liu, Gui-Bin; Yang, Shengyuan A.; Guo, Wei; Yao, Yugui

2018-01-01

Tuning band gaps of semiconductors in terms of defect control is essential for the optical and electronic properties of photon emission or photon harvesting devices. By using first-principles calculations, we study the stability condition of bulk CuInS2 and formation energies of point and complex defects in CuInS2 with hybrid exchange-correlation functionals. We find that at Cu-rich and In-poor conditions, 2Cui  +  CuIn is the main complex defect, while InCu  +  2VCu is the main complex defect at In-rich and Cu-poor conditions. Such stable complex defects provide the feasibility of tuning band gaps by varying the [Cu]/[In] molar ratios. These results present how the off-stoichiometry CuInS2 crystal structures, and electronic and optical properties can be optimized by tuning the [Cu]/[In] ratio and Fermi level, and highlight the importance of complex defects in achieving better photoelectric performance in CuInS2. Such band gap tuning in terms of complex defect engineering is a general approach and thus applicable to other photo-harvest or light-emission semiconductors.

Effect of fulvic and humic acids on copper and zinc homeostasis in rats.

PubMed

Hullár, István; Vucskits, András Valentin; Berta, Erzsébet; Andrásofszky, Emese; Bersényi, András; Szabó, József

2018-03-01

The objective of this study was to investigate the effects of fulvic acid (FA) and humic acid (HA), the two main compounds of humic substances (HSs), on copper (Cu) and zinc (Zn) homeostasis. Seventy-two male Wistar rats were randomly divided into nine experimental groups. The control diet (AIN-93G formula) and the diets supplemented with 0.1%, 0.2%, 0.4% and 0.8% FA or HA were fed for 26 days. Cu and Zn concentrations of the large intestinal content (LIC), liver, kidney, femur and hair were determined. FA and HA did not influence significantly the Cu or Zn contents of the experimental diets, the rats' feed intake, weight gain and the feed to gain ratio. Both FA and HA decreased the Cu concentrations of the LIC significantly and in a dose-related manner; however the absorption-stimulating effect of HA was more pronounced. FA increased the Cu content of the liver, but neither FA nor HA had a dose-dependent effect on it. FA or HA supplementations had no significant effect on the Cu concentration of the kidney. At the concentrations used, dietary FA or HA supplementations are not promising growth promoters. FA influences the Cu homeostasis unlike HA, because FA not only stimulates Cu absorption, but the extra quantity of absorbed Cu is retained in the organism. The stimulatory effect of HA on Zn absorption may not be manifested in Cu and Zn homeostasis, because of the tight connection of these microelements to FA and HA, which prevents the transmission of Zn from the ZnHA complex to the organs. As regards the effect of FA and HA on Cu and Zn homeostasis, both FA and HA stimulated the absorption of these microelements, but only FA increased the retention of Cu (in the liver) and Zn (in the kidney).

Influence of trace elements mixture on bacterial diversity and fermentation characteristics of liquid diet fermented with probiotics under air-tight condition.

PubMed

He, Yuyong; Chen, Zhiyu; Liu, Xiaolan; Wang, Chengwei; Lu, Wei

2014-01-01

Cu2+, Zn2+, Fe2+ and I- are often supplemented to the diet of suckling and early weaning piglets, but little information is available regarding the effects of different Cu2+, Zn2+, Fe2+ and I- mixtures on bacteria growth, diversity and fermentation characteristics of fermented liquid diet for piglets. Pyrosequencing was performed to investigate the effect of Cu2+, Zn2+, Fe2+ and I- mixtures on the diversity, growth and fermentation characteristics of bacteria in the liquid diet fermented with Bacillus subtilis and Enterococcus faecalis under air-tight condition. Results showed that the mixtures of Cu2+, Zn2+, Fe2+ and I- at different concentrations promoted Bacillus growth, increased bacterial diversity and lactic acid production and lowered pH to about 5. The importance of Cu2+, Zn2+, Fe2+ and I- is different for Bacillus growth with the order Zn2+> Fe2+>Cu2+> I- in a 21-d fermentation and Cu2+>I->Fe2+>Zn2+ in a 42-d fermentation. Cu2+, Zn2+, Fe2+ and I- is recommended at a level of 150, 60, 150 and 0.6 mg/kg respectively for the production of fermented liquid diet with Bacillus subtilis. The findings improve our understanding of the influence of trace elements on liquid diet fermentation with probiotics and support the proper use of trace elements in the production of fermented liquid diet for piglets.

Effects of Fabrication Parameters on Interface of Zirconia and Ti-6Al-4V Joints Using Zr55Cu30Al10Ni5 Amorphous Filler

NASA Astrophysics Data System (ADS)

Liu, Yuhua; Hu, Jiandong; Shen, Ping; Guo, Zuoxing; Liu, Huijie

2013-09-01

ZrO2 was brazed to Ti-6Al-4V using a Zr55Cu30Al10Ni5 (at.%) amorphous filler in a high vacuum at 1173-1273 K. The influences of brazing temperature, holding time, and cooling rate on the microstructure and shear strength of the joints were investigated. The interfacial microstructures can be characterized as ZrO2/ZrO2- x + TiO/(Zr,Ti)2(Cu,Ni)/(Zr,Ti)2(Cu,Ni,Al)/acicular Widmanstäten structure/Ti-6Al-4V. With the increase in the brazing temperature, both the thickness of the ZrO2- x + TiO layer and the content of the (Zr,Ti)2(Cu,Ni) phase decreased. However, the acicular Widmanstäten structure gradually increased. With the increase in the holding time, the (Zr,Ti)2(Cu,Ni) phase decreased, and the thickness of the (Zr,Ti)2(Cu,Ni) + (Zr,Ti)2(Cu,Ni,Al) layer decreased. In addition, cracks formed adjacent to the ZrO2 side under rapid cooling. The microstructures produced under various fabrication parameters directly influence the shear strength of the joints. When ZrO2 and Ti-6Al-4V couples were brazed at 1173 K for 10 min and then cooled at a rate of 5 K/min, the maximum shear strength of 95 MPa was obtained.

Surfactant-assisted hollowing of Cu nanoparticles involving halide-induced corrosion-oxidation processes.

PubMed

Huang, Chih-Chia; Hwu, Jih Ru; Su, Wu-Chou; Shieh, Dar-Bin; Tzeng, Yonhua; Yeh, Chen-Sheng

2006-05-03

We have demonstrated a simple fabrication of hollow nanoparticles by halide-induced corrosion oxidation with the aid of surfactants. Cuprous oxide Cu2O nanoshells can be generated by simply mixing Cu nanoparticles with alkyltrimethylammonium halides at 55 degrees C for 16 min. The hollowing mechanism proposed is that absorption of surfactants onto the Cu surface facilitates the formation of the void interior through an oxidative etching process. Upon extending the reaction up to 4 h, fragmentation, oxidation, and self-assembly were observed and the CuO ellipsoidal structures were formed. The headgroup lengths of the surfactants influenced the degree of CuO ellipsoidal formation, whereby longer surfactants favored the generation of ellipsoids. Optical absorption measured by UV-visible spectroscopy was used to monitor both oxidation courses of Cu-->Cu2O and Cu2O-->CuO and to determine the band-gap energies as 2.4 eV for Cu2O nanoshells and 1.89 eV for CuO ellipsoids. For the contact-angle measurements, the wettability changed from hydrophilicity (18 degrees) to hydrophobicity (140 degrees) as the Cu2O nanoshells shifted to CuO ellipsoids.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy.

PubMed

Niu, Shuqiang; Huang, Dao-Ling; Dau, Phuong D; Liu, Hong-Tao; Wang, Lai-Sheng; Ichiye, Toshiko

2014-03-11

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH 3 ) 2 ] 1-/0 , [Cu(NCS) 2 ] 1-/0 , [FeCl 4 ] 1-/0 , and [Fe(SCH 3 ) 4 ] 1-/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree-Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC- ω PBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy

PubMed Central

2015-01-01

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH3)2]1–/0, [Cu(NCS)2]1–/0, [FeCl4]1–/0, and [Fe(SCH3)4]1–/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree–Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC-ωPBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes. PMID:24803858

Efficient Destruction of Pollutants in Water by a Dual-Reaction-Center Fenton-like Process over Carbon Nitride Compounds-Complexed Cu(II)-CuAlO2.

PubMed

Lyu, Lai; Yan, Dengbiao; Yu, Guangfei; Cao, Wenrui; Hu, Chun

2018-04-03

Carbon nitride compounds (CN) complexed with the in-situ-produced Cu(II) on the surface of CuAlO 2 substrate (CN-Cu(II)-CuAlO 2 ) is prepared via a surface growth process for the first time and exhibits exceptionally high activity and efficiency for the degradation of the refractory pollutants in water through a Fenton-like process in a wide pH range. The reaction rate for bisphenol A removal is ∼25 times higher than that of the CuAlO 2 . According to the characterization, Cu(II) generation on the surface of CuAlO 2 during the surface growth process results in the marked decrease of the surface oxygen vacancies and the formation of the C-O-Cu bridges between CN and Cu(II)-CuAlO 2 in the catalyst. The electron paramagnetic resonance (EPR) analysis and density functional theory (DFT) calculations demonstrate that the dual reaction centers are produced around the Cu and C sites due to the cation-π interactions through the C-O-Cu bridges in CN-Cu(II)-CuAlO 2 . During the Fenton-like reactions, the electron-rich center around Cu is responsible for the efficient reduction of H 2 O 2 to • OH, and the electron-poor center around C captures electrons from H 2 O 2 or pollutants and diverts them to the electron-rich area via the C-O-Cu bridge. Thus, the catalyst exhibits excellent catalytic performance for the refractory pollutant degradation. This study can deepen our understanding on the enhanced Fenton reactivity for water purification through functionalizing with organic solid-phase ligands on the catalyst surface.

NO Chemisorption on Cu/SSZ-13: a Comparative Study from Infrared Spectroscopy and DFT Calculations

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

Zhang, Renqin; McEwen, Jean-Sabin; Kollar, Marton

The locations and energies of Cu ions in a Cu/SSZ-13 zeolite catalyst were investigated by density functional theory (DFT) calculations. For 'naked' Cu2+ ions (i.e., Cu2+ ions with no ligands in their coordination spheres other than zeolite lattice oxygen atoms), the more energetically favorable sites are within a 6-membered ring. However, with the presence of various adsorbates, the energy difference between 6- and 8-membered ring locations greatly diminishes. Specifically, Cu2+ ions are substantially stabilized by -OH ligands (as [CuII(OH)]+), making the extra-framework sites in an 8-membered ring energetically more favorable than 6-membered ring sites. Under fully dehydrated high vacuum conditionsmore » with different Si/Al and Cu/Al ratios, three chemisorbed NO species coexist upon exposure of NO to Cu/SSZ-13: NO+, Cu2+-NO and Cu+-NO. The relative signal intensities for these bands vary greatly with Si/Al ratios. The vibrational frequency of chemisorbed NO was found to be very sensitive to the location of Cu2+ ions. On the one hand, with the aid from DFT calculations, the nature for these vibrations can be assigned in detail. On the other hand, the relative intensities for various Cu2+-NO species provide a good measure of the nature of Cu2+ ions as functions of Si/Al and Cu/Al ratios and the presence of humidity. These new findings cast doubt on the generally accepted proposal that only Cu2+ ions located in 6-membered rings are catalytically active for NH3-SCR.« less

1,2,3-Triazole-Functionalized Polysulfone Synthesis through Microwave-Assisted Copper-Catalyzed Click Chemistry: A Highly Proton Conducting High Temperature Membrane.

PubMed

Sood, Rakhi; Donnadio, Anna; Giancola, Stefano; Kreisz, Aurélien; Jones, Deborah J; Cavaliere, Sara

2016-07-06

Microwave heating holds all the aces regarding development of effective and environmentally friendly methods to perform chemical transformations. Coupling the benefits of microwave-enhanced chemistry with highly reliable copper-catalyzed azide-alkyne cycloaddition (CuAAC) click chemistry paves the way for a rapid and efficient synthesis procedure to afford high performance thermoplastic materials. We describe herein fast and high yielding synthesis of 1,2,3-triazole-functionalized polysulfone through microwave-assisted CuAAC as well as explore their potential as phosphoric acid doped polymer electrolyte membranes (PEM) for high temperature PEM fuel cells. Polymers with various degrees of substitution of the side-chain functionality of 1,4-substituted 1,2,3-triazole with alkyl and aryl pendant structures are prepared by sequential chloromethylation, azidation, and microwave-assisted CuAAC using a range of alkynes (1-pentyne, 1-nonyne, and phenylacetylene). The completeness of reaction at each step and the purity of the clicked polymers were confirmed by (1)H-(13)C NMR, DOSY-NMR and FTIR-ATR spectroscopies. The thermal and thermochemical properties of the modified polymers were characterized by differential scanning calorimetry and thermogravimetric analysis coupled with mass spectroscopy (TG-MS), respectively. TG-MS analysis demonstrated that the commencement of the thermal degradation takes place with the decomposition of the triazole ring while its substituents have critical influence on the initiation temperature. Polysulfone functionalized with 4-phenyl-1,2,3-triazole demonstrates significantly higher Tg, Td, and elastic modulus than the ones bearing 4-propyl-1,2,3-triazole and 4-heptyl-1,2,3-triazole groups. After doping with phosphoric acid, the functionalized polymers with acid doping level of 5 show promising performance with high proton conductivity in anhydrous conditions (in the range of 27-35 mS/cm) and satisfactorily high elastic modulus (in the range of 332-349 MPa).

Fear-Conditioning Mechanisms Associated with Trait Vulnerability to Anxiety in Humans

PubMed Central

Indovina, Iole; Robbins, Trevor W.; Núñez-Elizalde, Anwar O.; Dunn, Barnaby D.; Bishop, Sonia J.

2011-01-01

Summary Investigations of fear conditioning in rodents and humans have illuminated the neural mechanisms underlying cued and contextual fear. A critical question is how personality dimensions such as trait anxiety act through these mechanisms to confer vulnerability to anxiety disorders, and whether humans' ability to overcome acquired fears depends on regulatory skills not characterized in animal models. In a neuroimaging study of fear conditioning in humans, we found evidence for two independent dimensions of neurocognitive function associated with trait vulnerability to anxiety. The first entailed increased amygdala responsivity to phasic fear cues. The second involved impoverished ventral prefrontal cortical (vPFC) recruitment to downregulate both cued and contextual fear prior to omission (extinction) of the aversive unconditioned stimulus. These two dimensions may contribute to symptomatology differences across anxiety disorders; the amygdala mechanism affecting the development of phobic fear and the frontal mechanism influencing the maintenance of both specific fears and generalized anxiety. PMID:21315265

Temperature-dependent ac conductivity and dielectric response of vanadium doped CaCu3Ti4O12 ceramic

NASA Astrophysics Data System (ADS)

Sen, A.; Maiti, U. N.; Thapa, R.; Chattopadhyay, K. K.

2011-09-01

Successful incorporation of vanadium dopant within the giant dielectric material CaCu 3Ti 4O12 (CCTO) through a conventional solid-state sintering process is achieved and its influence on the dielectric as well as electrical properties as a function of temperature and frequency is reported here. Proper crystalline phase formation together with dopant induced lattice constant shrinkage was confirmed through X-ray diffraction. The temperature dependence of the dielectric constant at different constant frequencies was investigated. We infer that the correlated barrier hopping (CBH) model is dominant in the conduction mechanism of the ceramic as per the temperature-dependent ac conductivity measurements. The electronic parameters such as density of the states at the Fermi level, N( E f) and hopping distance, R ω of the ceramic were also calculated using this model.

Neural correlates of behavioral preference for culturally familiar drinks.

PubMed

McClure, Samuel M; Li, Jian; Tomlin, Damon; Cypert, Kim S; Montague, Latané M; Montague, P Read

2004-10-14

Coca-Cola (Coke) and Pepsi are nearly identical in chemical composition, yet humans routinely display strong subjective preferences for one or the other. This simple observation raises the important question of how cultural messages combine with content to shape our perceptions; even to the point of modifying behavioral preferences for a primary reward like a sugared drink. We delivered Coke and Pepsi to human subjects in behavioral taste tests and also in passive experiments carried out during functional magnetic resonance imaging (fMRI). Two conditions were examined: (1) anonymous delivery of Coke and Pepsi and (2) brand-cued delivery of Coke and Pepsi. For the anonymous task, we report a consistent neural response in the ventromedial prefrontal cortex that correlated with subjects' behavioral preferences for these beverages. In the brand-cued experiment, brand knowledge for one of the drinks had a dramatic influence on expressed behavioral preferences and on the measured brain responses.

Gene duplication and neo-functionalization in the evolutionary and functional divergence of the metazoan copper transporters Ctr1 and Ctr2.

PubMed

Logeman, Brandon L; Wood, L Kent; Lee, Jaekwon; Thiele, Dennis J

2017-07-07

Copper is an essential element for proper organismal development and is involved in a range of processes, including oxidative phosphorylation, neuropeptide biogenesis, and connective tissue maturation. The copper transporter (Ctr) family of integral membrane proteins is ubiquitously found in eukaryotes and mediates the high-affinity transport of Cu + across both the plasma membrane and endomembranes. Although mammalian Ctr1 functions as a Cu + transporter for Cu acquisition and is essential for embryonic development, a homologous protein, Ctr2, has been proposed to function as a low-affinity Cu transporter, a lysosomal Cu exporter, or a regulator of Ctr1 activity, but its functional and evolutionary relationship to Ctr1 is unclear. Here we report a biochemical, genetic, and phylogenetic comparison of metazoan Ctr1 and Ctr2, suggesting that Ctr2 arose over 550 million years ago as a result of a gene duplication event followed by loss of Cu + transport activity. Using a random mutagenesis and growth selection approach, we identified amino acid substitutions in human and mouse Ctr2 proteins that support copper-dependent growth in yeast and enhance copper accumulation in Ctr1 -/- mouse embryonic fibroblasts. These mutations revert Ctr2 to a more ancestral Ctr1-like state while maintaining endogenous functions, such as stimulating Ctr1 cleavage. We suggest key structural aspects of metazoan Ctr1 and Ctr2 that discriminate between their biological roles, providing mechanistic insights into the evolutionary, biochemical, and functional relationships between these two related proteins. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Predicting As, Cd, Cu, Pb and Zn levels in grasses (Agrostis sp. and Poa sp.) and stinging nettle (Urtica dioica) applying soil-plant transfer models.

PubMed

Boshoff, Magdalena; De Jonge, Maarten; Scheifler, Renaud; Bervoets, Lieven

2014-09-15

The aim of this study was to derive regression-based soil-plant models to predict and compare metal(loid) (i.e. As, Cd, Cu, Pb and Zn) concentrations in plants (grass Agrostis sp./Poa sp. and nettle Urtica dioica L.) among sites with a wide range of metal pollution and a wide variation in soil properties. Regression models were based on the pseudo total (aqua-regia) and exchangeable (0.01 M CaCl2) soil metal concentrations. Plant metal concentrations were best explained by the pseudo total soil metal concentrations in combination with soil properties. The most important soil property that influenced U. dioica metal concentrations was the clay content, while for grass organic matter (OM) and pH affected the As (OM) and Cu and Zn (pH). In this study multiple linear regression models proved functional in predicting metal accumulation in plants on a regional scale. With the proposed models based on the pseudo total metal concentration, the percentage of variation explained for the metals As, Cd, Cu, Pb and Zn were 0.56%, 0.47%, 0.59%, 0.61%, 0.30% in nettle and 0.46%, 0.38%, 0.27%, 0.50%, 0.28% in grass. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity.

PubMed

Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

2015-11-23

Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

Potassium-induced effect on structure and chemical activity of Cu xO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study

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

Liu, Ping; An, Wei; Stacchiola, Dario

2015-10-16

Potassium (K) plays an essential role in promoting catalytic reaction in many established industrial catalytic processes. Here, we report a combined study using scanning tunneling microscopy (STM) and density functional theory (DFT) in understanding the effect of depositing K on the atomic and electronic structures as well as chemical activities of Cu xO/Cu(111) (x≤2). The DFT calculations observe a pseudomorphic growth of K on Cu xO/Cu(111) up to 0.19 monolayer (ML) of coverage, where K binds the surface via strong ionic interaction with chemisorbed oxygen and the relatively weak electrostatic interactions with copper ions, lower and upper oxygen on themore » Cu xO rings. The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K displays great impact on the surface electronic structure of Cu xO/Cu(111), which induces significant reduction in work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective. It varies depending on the nature of adsorbates. According to our results, K has little effect on surface acidity, while it enhances the surface basicity significantly. As a consequence, the presence of K does not help for CO adsorption on Cu xO/Cu(111), but being able to accelerate the activation of CO 2. Thus, such promotion strongly depends on the combinations from both geometric and electronic effects. Our results highlight the origin of promoting effect of alkalis in the design of catalysts for the complex reactions.« less

Endophytic bacteria take the challenge to improve Cu phytoextraction by sunflower.

PubMed

Kolbas, Aliaksandr; Kidd, Petra; Guinberteau, Jacques; Jaunatre, Renaud; Herzig, Rolf; Mench, Michel

2015-04-01

Endophytic bacteria from roots and crude seed extracts of a Cu-tolerant population of Agrostis capillaris were inoculated to a sunflower metal-tolerant mutant line, and their influence on Cu tolerance and phytoextraction was assessed using a Cu-contaminated soil series. Ten endophytic bacterial strains isolated from surface-sterilized A. capillaris roots were mixed to prepare the root endophyte inoculant (RE). In parallel, surface-sterilized seeds of A. capillaris were crushed in MgSO4 to prepare a crude seed extract containing seed endophytes (SE). An aliquot of this seed extract was filtered at 0.2 μm to obtain a bacterial cell-free seed extract (SEF). After surface sterilization, germinated sunflower seeds were separately treated with one of five modalities: no treatment (C), immersion in MgSO4 (CMg) or SEF solutions and inoculation with RE or SE. All plants were cultivated on a Cu-contaminated soil series (13-1020 mg Cu kg(-1)). Cultivable RE strains were mostly members of the Pseudomonas genera, and one strain was closely related to Labrys sp. The cultivable SE strains belonged mainly to the Bacillus genera and some members of the Rhodococcus genera. The treatment effects depended on the soil Cu concentration. Both SE and SEF plants had a higher Cu tolerance in the 13-517 mg Cu kg(-1) soil range as reflected by increased shoot and root DW yields compared to control plants. This was accompanied by a slight decrease in shoot Cu concentration and increase in root Cu concentration. Shoot and root DW yields were more promoted by SE than SEF in the 13-114 mg Cu kg(-1) soil range, which could reflect the influence of seed-located bacterial endophytes. At intermediate soil Cu (416-818 mg Cu kg(-1) soil), the RE and CMg plants had lower shoot Cu concentrations than the control, SE and SEF plants. At high total soil Cu (617-1020 mg Cu kg(-1)), root DW yield of RE plants slightly increased and their root Cu concentration rose by up to 1.9-fold. In terms of phytoextraction efficiency, shoot Cu removal was increased for sunflower plants inoculated with crude and bacterial cell-free seed extracts by 1.3- to 2.2-fold in the 13-416 mg Cu kg(-1) soil range. Such increase was mainly driven by an enhanced shoot DW yield. The number and distribution of endophytic bacteria in the harvested sunflower tissues must be further examined.

Single-phase and well-dispersed Cu1.75S nanocrystals by ambient pressure diethylene glycol solution synthesis

NASA Astrophysics Data System (ADS)

Zheng, Xuerong; Jin, Zhengguo; Liu, Hui; Wang, Yueqiu; Wang, Xin; Du, Haiyan

2013-02-01

Single-phase, well-dispersed Cu1.75S nanocrystals were synthesized by an ambient pressure, hydrazine hydrate and ethylenediamine co-assisted diethylene glycol based solution chemical process using copper chloride and thioacetamide as precursors at the temperature range from 180 to 210 °C. Influence of hydrazine hydrate and ethylenediamine adding amounts, synthetic temperature on crystal growth, size distribution and optical properties of the synthesized Cu1.75S nanocrystals were investigated by XRD, TEM, HRTEM, EDX and UV-vis measurements. The synthetic reaction at above 200 °C grew flaky-shaped nanocrystals with relatively narrow size distribution. The formation of single-phase Cu1.75S nanocrystals in the diethylene glycol based solution process might be involved in the presence of intermediate [Cu(en)n]1+ and [Cu(NH3)4]2+ complexes in reaction solution, providing a stable Cu(I) and Cu(II) valent-mixed precursor.

Pool boiling of water-Al2O3 and water-Cu nanofluids on horizontal smooth tubes

PubMed Central

2011-01-01

Experimental investigation of heat transfer during pool boiling of two nanofluids, i.e., water-Al2O3 and water-Cu has been carried out. Nanoparticles were tested at the concentration of 0.01%, 0.1%, and 1% by weight. The horizontal smooth copper and stainless steel tubes having 10 mm OD and 0.6 mm wall thickness formed test heater. The experiments have been performed to establish the influence of nanofluids concentration as well as tube surface material on heat transfer characteristics at atmospheric pressure. The results indicate that independent of concentration nanoparticle material (Al2O3 and Cu) has almost no influence on heat transfer coefficient while boiling of water-Al2O3 or water-Cu nanofluids on smooth copper tube. It seems that heater material did not affect the boiling heat transfer in 0.1 wt.% water-Cu nanofluid, nevertheless independent of concentration, distinctly higher heat transfer coefficient was recorded for stainless steel tube than for copper tube for the same heat flux density. PMID:21711741

Prediction of precipitate evolution and martensite transformation in Ti-Ni-Cu shape memory alloys by computational thermodynamics

NASA Astrophysics Data System (ADS)

Povoden-Karadeniz, A.; Cirstea, D. C.; Kozeschnik, E.

2016-04-01

Ti-50Ni to Ti-55Ni (at.%) can be termed as the pioneer of shape memory alloys (SMA). Intermetallic precipitates play an important role for strengthening. Their influence on the start temperature of the martensitic transformation is a crucial property for the shape memory effect. Efforts for increasing the martensite start temperature include replacement of a part of Ni atoms by Cu. The influence of Cu-addition to Ti-Ni SMA on T0- temperatures and the character of the austenite-martensite transformation is evaluated using a new thermodynamic database for the Ti-Ni-system extended by Cu. Trends of precipitation of intermetallic phases are simulated by combining the assessed thermodynamics of the Ti-Ni-Cu system with assessed diffusion mobility data and kinetic models, as implemented in the solid-state transformation software MatCalc and are presented in the form of time-temperature-precipitation diagrams. Thermodynamic equilibrium considerations, complemented by predictive thermo-kinetic precipitation simulation, facilitates SMA alloy design and definition of optimized aging conditions.

Ultrasound assisted co-precipitation of nanostructured CuO-ZnO-Al2O3 over HZSM-5: effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME.

PubMed

Allahyari, Somaiyeh; Haghighi, Mohammad; Ebadi, Amanollah; Hosseinzadeh, Shahin

2014-03-01

Nanostructured CuO-ZnO-Al2O3/HZSM-5 was synthesized from nitrate and acetate precursors using ultrasound assisted co-precipitation method under different irradiation powers. The CuO-ZnO-Al2O3/HZSM-5 nanocatalysts were characterized using XRD, FESEM, BET, FTIR and EDX Dot-mapping analyses. The results indicated precursor type and irradiation power have significant influences on phase structure, morphology, surface area and functional groups. It was observed that the acetate formulated CuO-ZnO-Al2O3/HZSM-5 nanocatalyst have smaller CuO crystals with better dispersion and stronger interaction between components in comparison to nitrate based nanocatalysts. Ultrasound assisted co-precipitation synthesis method resulted in nanocatalyst with more uniform morphology compared to conventional method and increasing irradiation power yields smaller particles with better dispersion and higher surface area. Additionally the crystallinity of CuO is lower at high irradiation powers leading to stronger interaction between metal oxides. The nanocatalysts performance were tested at 200-300 °C, 10-40 bar and space velocity of 18,000-36,000 cm(3)/g h with the inlet gas composition of H2/CO = 2/1 in a stainless steel autoclave reactor. The acetate based nanocatalysts irradiated with higher levels of power exhibited better reactivity in terms of CO conversion and DME yield. While there is an optimal temperature for CO conversion and DME yield in direct synthesis of DME, CO conversion and DME yield both increase with the pressure increase. Furthermore ultrasound assisted co-precipitation method yields more stable CuO-ZnO-Al2O3/HZSM-5 nanocatalyst while conventional precipitated nanocatalyst lost their activity ca. 18% and 58% in terms of CO conversion and DME yield respectively in 24 h time on stream test.

Elasto-plastic properties of Cu-Nb nanolaminate

NASA Astrophysics Data System (ADS)

Betekhtin, V. I.; Kolobov, Yu. R.; Kardashev, B. K.; Golosov, E. V.; Narykova, M. V.; Kadomtsev, A. G.; Klimenko, D. N.; Karpov, M. I.

2012-02-01

The Young's modulus, internal friction, and microplastic flow stress in Cu-Nb nanolaminate has been determined by an acoustic technique. The influence of high hydrostatic compression (1 GPa) on these elasto-plastic properties of the nanolaminate has been studied.

Mechanical properties of Zr41.2Ti13.8Ni10Cu12.5Be22.5 bulk metallic glass with different geometric confinements

NASA Astrophysics Data System (ADS)

Zhang, Changqin; Zhang, Haifeng; Sun, Qilei; Liu, Kegao

2018-03-01

Zr41.2Ti13.8Ni10Cu12.5Be22.5 (Vit 1) bulk metallic glass with Cu sleeves at different positions was prepared by the Cu mold casting method, and the effects of different geometric confinements offered by Cu sleeves on the mechanical properties of Vit 1 were investigated. It was found that the mechanical properties were prominently influenced by different geometric confinements and the plasticity could be modified by optimizing the positions of Cu sleeves. The results revealed that shear band initiation and propagation could be efficiently intervened by changing the radial boundary restraints, which led to quite different mechanical behaviors.

Influence of Selenization Time on Microstructural, Optical, and Electrical Properties of Cu2ZnGeSe4 Films

NASA Astrophysics Data System (ADS)

Swapna Mary, G.; Hema Chandra, G.; Anantha Sunil, M.; Gupta, Mukul

2018-01-01

We have studied the effects of selenization time on the microstructural, optical, and electrical properties of stacked (Cu/Se/ZnSe/Se/Ge/Se) × 4 layers to demonstrate growth of Cu2ZnGeSe4 (CZGSe) thin films. Electron beam evaporation was used to deposit CZGSe films on glass substrates for selenization in high vacuum at 450°C for different times (15 min, 30 min, 45 min, and 60 min). The incomplete reaction of the precursor layers necessitates selenization at higher temperature for different durations to achieve desirable microstructural and optoelectronic properties. Energy-dispersive spectroscopic measurements revealed that the stacked layers selenized at 450°C for 30 min were nearly stoichiometric with atomic ratios of Cu/(Zn + Ge) = 0.88, Zn/Ge = 1.11, and Se/(Cu + Zn + Ge) = 1.03. X-ray diffraction analysis revealed that the stacks selenized at 450°C for 30 min crystallized in tetragonal stannite structure. Selenization-time-dependent Raman measurements of the selenized stacks are systematically presented to understand the growth of CZGSe. The elemental distribution through depth as a function of selenization time was investigated using secondary-ion mass spectroscopy. The ionic valency of the constituent elements in CZGSe films selenized at 450°C for 30 min was examined using high-resolution x-ray photoelectron spectroscopy. Significant changes were observed in the surface morphology of the stacked layers with increase in selenization time. The effects of defects on the electrical properties and of binary phases on the optical properties are discussed.

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

DOE PAGES

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra; ...

2017-07-24

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

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

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

Removal of Cu(II) in water by polymer enhanced ultrafiltration: Influence of polymer nature and pH.

PubMed

Kochkodan, Olga D; Kochkodan, Viktor M; Sharma, Virender K

2018-01-02

This study presents an efficient removal of Cu(II) in water using the polymer enhanced ultrafiltration (PEUF) method. Polymer of different molecular weight (MW) (polyethyleneimine (PEI), sodium lignosulfonates (SLS) and dextrans) were investigated to evaluate efficiency in removal of Cu(II) in water by the PEUF method. The decomposition of Cu(II)-polymer complex was also evaluated in order to reuse polymers. Cu(II) complexation depends on the MW of chelating polymer and the pH of feed solution. It was found that the Cu(II) rejection increased with the polymer dosage with high removal of Cu(II) when using PEI and SLS at a 10:20 (mg/mg) ratio ([Cu(II)]:[polymer]). It was found that the maximum chelating capacity was 15 mg of Cu(II) per 20 mg of PEI. The Cu(II)-PEI complex could be decomposed by acid addition and the polymer could be efficiently reused with multiple complexation-decomplexation cycles. A conceptual flow chart of the integrated process of efficient removal of Cu(II) by PEUF method is suggested.

Directing the Branching Growth of Cuprous Oxide by OH- Ions

NASA Astrophysics Data System (ADS)

Chen, Kunfeng; Si, Yunfei; Xue, Dongfeng

The effect of OH- ions on the branching growth of cuprous oxide microcrystals was systematically studied by a reduction route, where copper-citrate complexes were reduced by glucose under alkaline conditions. Different copper salts including Cu(NO3)2, CuCl2, CuSO4, and Cu(Ac)2 were used in this work. The results indicate that the Cu2O branching growth habit is closely correlated to the concentration of OH- ions, which plays an important role in directing the diffusion-limited branching growth of Cu2O and influencing the reduction power of glucose. A variety of Cu2O branching patterns including 6-pod, 8-pod and 24-pod branches, have been achieved without using template and surfactant. The current method can provide a good platform for studying the growth mechanism of microcrystal branching patterns.

Electronic π-Delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets.

PubMed

Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Moonshiram, Dooshaye; Picón, Antonio; Monge, Pere; Batista, Victor S; Llobet, Antoni

2017-09-20

A molecular water oxidation catalyst based on the copper complex of general formula [(L py )Cu II ] 2- , 2 2- , (L py is 4-pyrenyl-1,2-phenylenebis(oxamidate) ligand) has been rationally designed and prepared to support a more extended π-conjugation through its structure in contrast with its homologue, the [(L)Cu II ] 2- water oxidation catalyst, 1 2- (L is o-phenylenebis(oxamidate)). The catalytic performance of both catalysts has been comparatively studied in homogeneous phase and in heterogeneous phase by π-stacking anchorage to graphene-based electrodes. In the homogeneous system, the electronic perturbation provided by the pyrene functionality translates into a 150 mV lower overpotential for 2 2- with respect to 1 2- and an impressive increase in the k cat from 6 to 128 s -1 . Upon anchorage, π-stacking interactions with the graphene sheets provide further π-delocalization that improves the catalytic performance of both catalysts. In this sense, 2 2- turned out to be the most active catalyst due to the double influence of both the pyrene and the graphene, displaying an overpotential of 538 mV, a k cat of 540 s -1 and producing more than 5300 TONs.

Multivariate methods for evaluating the efficiency of electrodialytic removal of heavy metals from polluted harbour sediments.

PubMed

Pedersen, Kristine Bondo; Kirkelund, Gunvor M; Ottosen, Lisbeth M; Jensen, Pernille E; Lejon, Tore

2015-01-01

Chemometrics was used to develop a multivariate model based on 46 previously reported electrodialytic remediation experiments (EDR) of five different harbour sediments. The model predicted final concentrations of Cd, Cu, Pb and Zn as a function of current density, remediation time, stirring rate, dry/wet sediment, cell set-up as well as sediment properties. Evaluation of the model showed that remediation time and current density had the highest comparative influence on the clean-up levels. Individual models for each heavy metal showed variance in the variable importance, indicating that the targeted heavy metals were bound to different sediment fractions. Based on the results, a PLS model was used to design five new EDR experiments of a sixth sediment to achieve specified clean-up levels of Cu and Pb. The removal efficiencies were up to 82% for Cu and 87% for Pb and the targeted clean-up levels were met in four out of five experiments. The clean-up levels were better than predicted by the model, which could hence be used for predicting an approximate remediation strategy; the modelling power will however improve with more data included. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of oxygen vacancy on the electronic structure of CaCu3Ti4O12 and its deep-level vacancy trap states by first-principle calculation

NASA Astrophysics Data System (ADS)

Xiao, H. B.; Yang, C. P.; Huang, C.; Xu, L. F.; Shi, D. W.; Marchenkov, V. V.; Medvedeva, I. V.; Bärner, K.

2012-03-01

The electronic structure, formation energy, and transition energy levels of intrinsic defects have been studied using the density-functional method within the generalized gradient approximation for neutral and charged oxygen vacancy in CaCu3Ti4O12 (CCTO). It is found that oxygen vacancies with different charge states can be formed in CCTO under both oxygen-rich and poor conditions for nonequilibrium and higher-energy sintering processes; especially, a lower formation energy is obtained for poor oxygen environment. The charge transition level (0/1+) of the oxygen vacancy in CCTO is located at 0.53 eV below the conduction-band edge. The (1+/2+) transition occurs at 1.06 eV below the conduction-band edge. Oxygen vacancies of Vo1+ and Vo2+ are positive stable charge states in most gap regions and can act as a moderately deep donor for Vo1+ and a borderline deep for Vo2+, respectively. The polarization and dielectric constant are considerably enhanced by oxygen vacancy dipoles, due to the off-center Ti and Cu ions in CCTO.

The Impact of Seed Layer Structure on the Recrystallization of ECD Cu and its Alloys

NASA Astrophysics Data System (ADS)

O'Brien, Brendan B.

Despite the significant improvements originally offered by the use of Cu over Al as the interconnect material for semiconductor devices, the continued down-scaling of interconnects has presented significant challenges for semiconductor engineers. As the metal line widths shrink, both the conductivity and reliability of lines decrease due to a stubbornly fine-grained microstructure in narrow lines. Understanding microstructural transformation of the ECD Cu in narrow features which leads to this polygranular microstructure is the first focus of this dissertation. As in the case of Cu films, the underlying seed layer strongly influences progress of transformation. Unlike films, however, the seed layer is not homogenous in patterned substrates, but differs according to the size of the trench and the location within the trench (field, bottom, and sidewall). Based on these findings, and the known influence of texture on the transformation of ECD Cu, a rapid trench initiated transformation process was posited for narrow interconnect lines. Time-resolved TEM observation of the ECD Cu in 48 nm lines during the transformation process confirmed the hypothesis. In fact, the TEM images revealed that the transformation was even faster than anticipated, and that the microstructure of the Cu inside the lines was stagnant after a mere 1.5 hours at room temperature. Studies of the transformation at elevated temperatures found that, despite anneals at 250°C for up to an hour, the grain size distribution for the Cu in narrow lines for all times converged, whether annealed at room temperature or 250°C. These data suggest that process was being driven by the 'consumable' internal energy stored in the as-plated microstructure. This is different than the transformation of the overburden, which is driven by a competition between surface energy and internal stress buildup due to film densification and relief due to the secondary growth of a 200 texture component. Based on these findings, two methods for manipulating the microstructure of the ECD Cu in the narrow lines were explored, including changes to the seed layer through ion implantation, and altering the as-plated Cu microstructure through co-ECD of alloys. The influence on the microstructure and applicability of both of these techniques to BEOL processing will also be discussed.

Copper(II) and zinc(II) dinuclear enzymes model compounds: The nature of the metal ion in the biological function

NASA Astrophysics Data System (ADS)

Ferraresso, L. G.; de Arruda, E. G. R.; de Moraes, T. P. L.; Fazzi, R. B.; Da Costa Ferreira, A. M.; Abbehausen, C.

2017-12-01

First series transition metals are used abundantly by nature to perform catalytic transformations of several substrates. Furthermore, the cooperative activity of two proximal metal ions is common and represents a highly efficient catalytic system in living organisms. In this work three dinuclear μ-phenolate bridged metal complexes were prepared with copper(II) and zinc(II), resulting in a ZnZn, CuCu and CuZn with the ligand 2-ethylaminodimethylamino phenol (saldman) as model compounds of superoxide dismutase (CuCu and CuZn) and metallo-β-lactamases (ZnZn). Metals are coordinated in a μ-phenolate bridged symmetric system. Cu(II) presents a more distorted structure, while zinc is very symmetric. For this reason, [CuCu(saldman)] shows higher water solubility and also higher lability of the bridge. The antioxidant and hydrolytic beta-lactamase-like activity of the complexes were evaluated. The lability of the bridge seems to be important for the antioxidant activity and is suggested to because of [CuCu(saldman)] presents a lower antioxidant capacity than [CuZn(saldman)], which showed to present a more stable bridge in solution. The hydrolytic activity of the bimetallic complexes was assayed using nitrocefin as substrate and showed [ZnZn(saldman)] as a better catalyst than the Cu(II) analog. The series demonstrates the importance of the nature of the metal center for the biological function and how the reactivity of the model complex can be modulated by coordination chemistry.

Effect of Cu Salt Molarity on the Nanostructure of CuO Prolate Spheroid

NASA Astrophysics Data System (ADS)

Sabeeh, Sabah H.; Hussein, Hashim Abed; Judran, Hadia Kadhim

Copper sulfate pentahydrate was used as a source of Cu ion with five different molarities (0.02, 0.05, 0.1, 0.15, 2 and 0.25M). XRD, FE-SEM and TEM techniques all showed that CuO samples have polycrystalline monoclinic structure. CuO prolate spheroid is assembled from nanoparticles as building units. It was demonstrated that the purity, morphology, size range of prolate spheroid and density of nano building units are significantly influenced by Cu precursor’s molarity. The pure phase of CuO prolate spheroid was produced via molarity of 0.2M with crystallite size of 15.1565nm while the particle size of building units ranges from 16nm to 21nm. The stability of CuO nanosuspension or nanofluid was evaluated by zeta potential analysis. The obtained properties of specific structure with large surface area of CuO prolate spheroid make it a promising candidate for wide range of potential applications as in nanofluids for cooling purposes.

Copper-induced ammonia N-H functionalization.

PubMed

Álvarez, María; Álvarez, Eleuterio; Fructos, Manuel R; Urbano, Juan; Pérez, Pedro J

2016-10-07

The activation of ammonia has been achieved with the aid of the Tp(Ms)Cu core (Tp(Ms) = hydrotris(3-mesityl-pyrazolyl)borate). Complexes of the general composition Tp(Ms)Cu(amine) (1-4) including the ammonia adduct Tp(Ms)Cu(NH3) (1) have been synthesized and fully spectroscopical- and structurally characterized. Coordinated ammonia in 1 has been reacted with Ph3CPF6 yielding Tp(Ms)Cu(NH2CPh3) (5) as a result of N-H cleavage and N-C bond formation. In a parallel manner the catalytic functionalization of ammonia with ethyl diazoacetate leading to glycinate derivatives has been developed with Tp(Ms)Cu(THF) as the catalyst, in the first example of this transformation with ammonia and a copper-based system.

Effects of the molecule-electrode interface on the low-bias conductance of Cu–H{sub 2}–Cu single-molecule junctions

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

Jiang, Zhuoling; Centre for Nanoscale Science and Technology, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871; Wang, Hao

The atomic structure and electronic transport properties of a single hydrogen molecule connected to both symmetric and asymmetric Cu electrodes are investigated by using the non-equilibrium Green’s function formalism combined with the density functional theory. Our calculations show that in symmetric Cu–H{sub 2}–Cu junctions, the low-bias conductance drops rapidly upon stretching, while asymmetric ones present a low-bias conductance spanning the 0.2–0.3 G{sub 0} interval for a wide range of electrode separations. This is in good agreement with experiments on Cu atomic contacts in a hydrogen environment. Furthermore, the distribution of the calculated vibrational energies of the two hydrogen atoms inmore » the asymmetric Cu–H{sub 2}–Cu junction is also consistent with experiments. These findings provide clear evidence for the formation of asymmetric Cu–H{sub 2}–Cu molecular junctions in breaking Cu atomic contacts in the presence of hydrogen and are also helpful for the design of molecular devices with Cu electrodes.« less

Atomic scale real-space mapping of holes in YBa2Cu3O(6+δ).

PubMed

Gauquelin, N; Hawthorn, D G; Sawatzky, G A; Liang, R X; Bonn, D A; Hardy, W N; Botton, G A

2014-07-15

The high-temperature superconductor YBa2Cu3O(6+δ) consists of two main structural units--a bilayer of CuO2 planes that are central to superconductivity and a CuO(2+δ) chain layer. Although the functional role of the planes and chains has long been established, most probes integrate over both, which makes it difficult to distinguish the contribution of each. Here we use electron energy loss spectroscopy to directly resolve the plane and chain contributions to the electronic structure in YBa2Cu3O6 and YBa2Cu3O7. We directly probe the charge transfer of holes from the chains to the planes as a function of oxygen content, and show that the change in orbital occupation of Cu is large in the chain layer but modest in CuO2 planes, with holes in the planes doped primarily into the O 2p states. These results provide direct insight into the local electronic structure and charge transfers in this important high-temperature superconductor.

In situ study of heavy ion irradiation response of immiscible Cu/Fe multilayers

DOE PAGES

Chen, Youxing; Li, Nan; Bufford, Daniel Charles; ...

2016-04-09

By providing active defect sinks that capture and annihilate radiation induced defect clusters immiscible metallic multilayers with incoherent interfaces can effectively reduce defect density in ion irradiated metals. Although it is anticipated that defect density within the layers should vary as a function of distance to the layer interface, there is, to date, little in situ TEM evidence to validate this hypothesis. In our study monolithic Cu films and Cu/Fe multilayers with individual layer thickness, h, of 100 and 5 nm were subjected to in situ Cu ion irradiation at room temperature to nominally 1 displacement-per-atom inside a transmission electronmore » microscope. Rapid formation and propagation of defect clusters were observed in monolithic Cu, whereas fewer defects with smaller dimensions were generated in Cu/Fe multilayers with smaller h. Moreover, in situ video shows that the cumulative defect density in Cu/Fe 100 nm multilayers indeed varies, as a function of distance to the layer interfaces, supporting a long postulated hypothesis.« less

Intestinal Alterations, Basal Hematology, and Biochemical Parameters in Adolescent Rats Fed Different Sources of Dietary Copper.

PubMed

Tomaszewska, Ewa; Dobrowolski, Piotr; Kwiecień, Małgorzata

2016-05-01

Copper (Cu) is required for basically all biochemical and physiological processes in the body. The aim was to evaluate the effects of different sources of dietary copper on jejunal epithelium histomorphometry in adolescent rats. Male rats at the age of 5 weeks were used in the 12-week experiment. The control group was fed with standard diet providing the required Cu level (5 mg/kg body weight (bw) per day) in an inorganic form (sulfate) covered 100 % of daily demand, and the other three groups were supplemented with Cu-glycine complex covered 50, 75, and 100 % daily demand. Basal hematological and plasma biochemical analyses as well as histomorphometric examinations of the jejunal epithelium and liver were performed. Cu given in the organic form in 100 % of daily demand depressed the muscular and submucosa layer and the crypt depth (P < 0.05) without an influence of the innervation of the jejunum. In turn, organic Cu given in 75 % of daily demand did not influence the intestinal morphology in adult rats. Dietary organic Cu given to rats covering the daily demand in 50 or 75 % appears to be less harmful with regard to the intestinal epithelium than when administered in 100 % of daily demand.

Study of the influence of different organic pollutants on Cu accumulation by Halimione portulacoides

NASA Astrophysics Data System (ADS)

Almeida, C. Marisa R.; Claúdia Dias, A.; Mucha, Ana P.; Bordalo, A. A.; Vasconcelos, M. Teresa S. D.

2009-12-01

The influence of each of four organic pollutants selected from among those commonly found in coastal areas, 1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene (DDE), monobutyltin (MBT), Triton X-100 and polycyclic aromatic hydrocarbons (PAHs), on Cu accumulation by Halimione portulacoides was investigated. Experiments were carried out in a laboratory setting, either in hydroponics (sediment elutriate) or in a salt marsh sediment ( Cávado River, NW Portugal) soaked in elutriate. Groups of H. portulacoides were exposed to media for 6 days spiked with 10 mg/L Cu(II) and with one of the selected pollutants, at an environmentally realistic concentration. DDE and MBT did not cause any major change on Cu accumulation by H. portulacoides, whereas PAHs slightly increased accumulation only in hydroponics i.e. in the absence of sediment. On the other hand, the non-ionic surfactant Triton X-100 markedly favoured Cu accumulation on plant roots both in the presence and absence of sediment. The addition of DDE, MBT and Triton X-100 also favoured Cu solubility from sediments. Therefore, the simultaneous presence of pollutants from different nature (inorganic and organic) in the estuarine environment may result in a composition of water column, pore water, sediment or biota different of that expected considering the effect of each individual pollutant.

Metal-ligand delocalization and spin density in the CuCl2 and [CuCl4](2-) molecules: Some insights from wave function theory.

PubMed

Giner, Emmanuel; Angeli, Celestino

2015-09-28

The aim of this paper is to unravel the physical phenomena involved in the calculation of the spin density of the CuCl2 and [CuCl4](2-) systems using wave function methods. Various types of wave functions are used here, both variational and perturbative, to analyse the effects impacting the spin density. It is found that the spin density on the chlorine ligands strongly depends on the mixing between two types of valence bond structures. It is demonstrated that the main difficulties found in most of the previous studies based on wave function methods come from the fact that each valence bond structure requires a different set of molecular orbitals and that using a unique set of molecular orbitals in a variational procedure leads to the removal of one of them from the wave function. Starting from these results, a method to compute the spin density at a reasonable computational cost is proposed.

Undercooling Behavior and Intermetallic Compound Coalescence in Microscale Sn-3.0Ag-0.5Cu Solder Balls and Sn-3.0Ag-0.5Cu/Cu Joints

NASA Astrophysics Data System (ADS)

Zhou, M. B.; Ma, X.; Zhang, X. P.

2012-11-01

The microstructure of microscale solder interconnects and soldering defects have long been known to have a significant influence on the reliability of electronic packaging, and both are directly related to the solidification behavior of the undercooled solder. In this study, the undercooling behavior and solidification microstructural evolution of Sn-3.0Ag-0.5Cu solder balls with different diameters (0.76 mm, 0.50 mm, and 0.30 mm) and the joints formed by soldering these balls on Cu open pads of two diameters (0.48 mm and 0.32 mm) on a printed circuit board (PCB) substrate were characterized by differential scanning calorimetry (DSC) incorporated into the reflow process. Results show that the decrease in diameter of the solder balls leads to an obvious increase in the undercooling of the balls, while the undercooling of the solder joints shows a dependence on both the diameter of the solder balls and the diameter ratio of solder ball to Cu pad (i.e., D s/ D p), and the diameter of the solder balls has a stronger influence on the undercooling of the joints than the dimension of the Cu pad. Coarse primary intermetallic compound (IMC) solidification phases were formed in the smaller solder balls and joints. The bulk Ag3Sn IMC is the primary solidification phase in the as-reflowed solder balls. Due to the interfacial reaction and dissolution of Cu atoms into the solder matrix, the primary Ag3Sn phase can be suppressed and the bulk Cu6Sn5 IMC is the only primary solidification phase in the as-reflowed solder joints.

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.

Two-photon momentum density in La2-xSrxCuO4 and Nd2-xCexCuO4

NASA Astrophysics Data System (ADS)

Blandin, P.; Massidda, S.; Barbiellini, B.; Jarlborg, T.; Lerch, P.; Manuel, A. A.; Hoffmann, L.; Gauthier, M.; Sadowski, W.; Walker, E.; Peter, M.; Yu, Jaejun; Freeman, A. J.

1992-07-01

We present calculations of the electron-positron momentum density for the high-Tc superconductors La2-xSrxCuO4 and Nd2-xCexCuO4, together with experimental two-dimensional angular correlation of annihilation radiation (2D-ACAR) for Nd2-xCexCuO4. The calculations are based on first-principles electronic structure obtained using the full-potential linearized augmented-plane-wave and the linear muffin-tin orbital methods. Our results indicate a non-negligible overlap of the positron wave function with the CuO2 plane electrons responsible for the Fermi surfaces in these compounds. Therefore, these compounds may be well suited for investigating Fermi-surface-related effects. After the folding of umklapp terms according to Lock, Crisp, and West, the predicted Fermi-surface breaks are mixed with strong effects induced by the positron wave function in La2-xSrxCuO4, while their resolution is better in Nd2-xCexCuO4. A comparison of our calculations with the most recent experimental results for La2-xSrxCuO4 shows good agreement. For Nd2-xCexCuO4 good agreement is observed between theoretical and experimental 2D-ACAR profiles.

Impaired holistic processing of left-right composite faces in congenital prosopagnosia.

PubMed

Liu, Tina T; Behrmann, Marlene

2014-01-01

Congenital prosopagnosia (CP) refers to a lifelong impairment in face processing despite normal visual and intellectual skills. Many studies have suggested that the key underlying deficit in CP is one of a failure to engage holistic processing. Moreover, there has been some suggestion that, in normal observers, there may be greater involvement of the right than left hemisphere in holistic processing. To examine the proposed deficit in holistic processing and its potential hemispheric atypicality in CP, we compared the performance of 8 CP individuals with both matched controls and a large group of non-matched controls on a novel, vertical composite task. In this task, participants judged whether a cued half of a face (either left or right half) was the same or different at study and test, and the two face halves could be either aligned or misaligned. The standard index of holistic processing is one in which the unattended face half influences performance on the cued half and this influence is greater in the aligned than in the misaligned condition. Relative to controls, the CP participants, both at a group and at an individual level, did not show holistic processing in the vertical composite task. There was also no difference in performance as a function of hemifield of the cued face half in the CP individuals, and this was true in the control participants, as well. The findings clearly confirm the deficit in holistic processing in CP and reveal the useful application of this novel experimental paradigm to this population and potentially to others as well.

Influence of stacking fault energy on defect structures and microhardness of Cu and Cu alloys.

PubMed

Tao, Jing-Mei; Li, Dai; Li, Cai-Ju; Zhu, Xin-Kun

2011-12-01

Nano-structured Cu, Cu-10 wt%Zn and Cu-2 wt%Al with stacking fault energies (SFE) of 78, 35 and 37 mJ/m2, respectively, were preprared through high energy ball milling. X-ray diffraction and Vickers microharness test were used to investigate the microstructure and microhardness of all the samples after ball milling. X-ray diffraction measurements indicate that lower SFEs lead both to decrease in grain size and increase in microstrain, dislocation and twin densities for Cu-10 wt%Zn and Cu-2 wt%Al after 5 h of ball milling. The microhardnesses of Cu-10 wt%Zn and Cu-2 wt%Al reach to nearly the same values of 2.5 GPa after 5 h of ball milling, which is higher than that of Cu of 2.0 GPa. Two factors are considered to contribute to the finer grian size and higher microhardness of Cu-10 wt%Zn and Cu-2 wt%Al: (1) the effect of solid solution strengthening, which result in the interaction of solute atoms with screw dislocations; (2) the introduction of deformation twins during ball milling process by the decreasing of SFE, which results in the grain refinement.

Ti Impurity Effect on the Optical Coefficients in 2D Cu2Si: A DFT Study

NASA Astrophysics Data System (ADS)

Nourozi, Bromand; Boochani, Arash; Abdolmaleki, Ahmad; Sartpi, Elmira; Darabi, Pezhman; Naderi, Sirvan

2018-01-01

The electronic and optical properties of 2D Cu2Si and Cu2Si:Ti are investigated based on the density functional theory (DFT) using the FP-LAPW method and GGA approximation. The 2D Cu2Si has metallic and non magnetic properties, whereas adding Ti impurity to its structure changes the electronic behavior to the half-metallic with 3.256μB magnetic moment. The optical transition is not occurred in the infrared and visible area for the 2D Cu2Si in x-direction and by adding Ti atom, the real part of dielectric function in the x-direction, Re (ε(ω))x is reached to a Dirac peak at this energy range. Moreover, the absorption gap tends to zero in x-direction of the 2D Cu2Si:Ti. Supported by Islamic Azad University, Kermanshah branch, Kermanshah, Iran

Functional characterisation of Arabidopsis SPL7 conserved protein domains suggests novel regulatory mechanisms in the Cu deficiency response.

PubMed

Garcia-Molina, Antoni; Xing, Shuping; Huijser, Peter

2014-08-30

The Arabidopsis SQUAMOSA PROMOTER-BINDING PROTEIN-LIKE (SPL) transcription factor SPL7 reprograms cellular gene expression to adapt plant growth and cellular metabolism to copper (Cu) limited culture conditions. Plant cells require Cu to maintain essential processes, such as photosynthesis, scavenging reactive oxygen species, cell wall lignification and hormone sensing. More specifically, SPL7 activity promotes a high-affinity Cu-uptake system and optimizes Cu (re-)distribution to essential Cu-proteins by means of specific miRNAs targeting mRNA transcripts for those dispensable. However, the functional mechanism underlying SPL7 activation is still to be elucidated. As SPL7 transcript levels are largely non-responsive to Cu availability, post-translational modification seems an obvious possibility. Previously, it was reported that the SPL7 SBP domain does not bind to DNA in vitro in the presence of Cu ions and that SPL7 interacts with a kin17 domain protein to raise SPL7-target gene expression upon Cu deprivation. Here we report how additional conserved SPL7 protein domains may contribute to the Cu deficiency response in Arabidopsis. Cytological and biochemical approaches confirmed an operative transmembrane domain (TMD) and uncovered a dual localisation of SPL7 between the nucleus and an endomembrane system, most likely the endoplasmic reticulum (ER). This new perspective unveiled a possible link between Cu deficit and ER stress, a metabolic dysfunction found capable of inducing SPL7 targets in an SPL7-dependent manner. Moreover, in vivo protein-protein interaction assays revealed that SPL7 is able to homodimerize, probably mediated by the IRPGC domain. These observations, in combination with the constitutive activation of SPL7 targets, when ectopically expressing the N-terminal part of SPL7 including the SBP domain, shed some light on the mechanisms governing SPL7 function. Here, we propose a revised model of SPL7 activation and regulation. According to our results, SPL7 would be initially located to endomembranes and activated during ER stress as a result of Cu deficiency. Furthermore, we added the SPL7 dimerization in the presence of Cu ions as an additional regulatory mechanism to modulate the Cu deficiency response.

Synthesis of CuPF6 -(S)-BINAP loaded resin and its enantioselectivity toward phenylalanine enantiomers.

PubMed

Liu, Xiong; Zhou, Wenqi; Xu, Longqi

2017-09-01

A type of resin-anchored CuPF 6 -(S)-BINAP was synthesized and identified. The PS-CuPF 6 -(S)-BINAP resin was used to adsorb the phenylalanine enantiomers. The results showed that the adsorption capacity of PS-CuPF 6 -(S)-BINAP resin toward L-phenylalanine was higher than that of resin toward D-phenylalanine. PS-CuPF 6 -(S)-BINAP resin exhibited good enantioselectivity toward L-phenylalanine and D-phenylalanine. The influence of phenylalanine concentration, pH, adsorption time, and temperature on the enantioselectivity of the resin were investigated. The results showed that the enantioselectivity of the resin increased with increasing the phenylalanine concentration, pH, and adsorption time, while it decreased with an increase in temperature. The causes for these influences are discussed. The highest enantioselectivity (α = 2.81) was obtained when the condition of phenylalanine concentration was 0.05 mmol/mL, pH was 8, adsorption time was 12 h, and temperature 5°C. The desorption test for removing D/L-phenylalanine on PS-CuPF 6 -(S)-BINAP resin was also investigated. The desorption ratios of D-phenylalanine and L-phenylalanine at pH of 1 were 95.7% and 94.3%, respectively. This result indicated that the PS-CuPF 6 -(S)-BINAP resin could be regenerated by shaking with an acidic solution. The reusability of the PS-CuPF 6 -(S)-BINAP resin was also assessed and the resin exhibited considerable reusability. © 2017 Wiley Periodicals, Inc.

The influence of liming on soil chemical properties and on the alleviation of manganese and copper toxicity in Juglans regia, Robinia pseudoacacia, Eucalyptus sp. and Populus sp. plantations.

PubMed

Chatzistathis, T; Alifragis, D; Papaioannou, A

2015-03-01

Juglans regia, Robinia pseudoacacia, Eucalyptus sp. and Populus sp. plantations, suffering from Mn and Cu toxicity, were limed in order to reduce Cu and Mn solubility in soil. The purposes of the present work were: i) to study the changes in soil chemical properties after the addition of CaCO3, ii) to investigate the influence of liming on the reduction of Mn and Cu toxicity. After the addition of CaCO3 (three applications, during three successive years), pH and CaCO3 content were significantly increased, while organic C and N were significantly reduced. Exchangeable Ca concentrations have been slightly, or significantly, increased, while those of Mg have been decreased; in addition, ratios Ca/Mg and C/N have been significantly increased after liming. Impressive reductions of DTPA extractable Cu and Mn concentrations (more than 10 times in most cases) were recorded. It was also found that trees without Mn and Cu toxicity symptoms (healthy tress) before liming did not have, in many cases, significantly greater leaf Mn, Cu and Fe concentrations, than trees after soil liming (all the trees were healthy). This probably happened because excess Mn and Cu quantities had been accumulated into their root system. Finally, leaf Mn, Cu and Zn concentrations of trees suffering from toxicity were significantly decreased after soil liming, while leaf Fe concentrations, in all the plant species studied, were increased. Copyright © 2014 Elsevier Ltd. All rights reserved.

Endothelial Antioxidant-1: A key mediator of Copper-dependent wound healing in vivo

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

Das, Archita; Sudhahar, Varadarajan; Chen, Gin -Fu

Here, Copper (Cu), an essential nutrient, promotes wound healing, however, target of Cu action and underlying mechanisms remains elusive. Cu chaperone Antioxidant-1 (Atox1) in the cytosol supplies Cu to the secretory enzymes such as lysyl oxidase (LOX) while Atox1 in the nucleus functions as a Cu-dependent transcription factor. Using cutaneous wound healing model, here we show that Cu content (by X-ray Fluorescence Microscopy) and nuclear Atox1 are increased after wounding, and that wound healing with and without Cu treatment is impaired in Atox1 -/ - mice. Experiments using endothelial cell (EC)-specific Atox1 -/ - mice and gene transfer of nuclear-targetmore » Atox1 in Atox1 -/ - mice reveal that Atox1 in ECs as well as transcription factor function of Atox1 are required for wound healing. Mechanistically, Atox1 -/ - mice show reduced Atox1 target proteins such as p47phox NADPH oxidase and cyclin D1 as well as extracellular matrix Cu enzyme LOX activity in wound tissues. This in turn results in reducing O 2 - production in ECs, NFkB activity, cell proliferation and collagen formation, thereby inhibiting angiogenesis, macrophage recruitment and extracellular matrix maturation. Our findings suggest that Cu-dependent transcription factor/Cu chaperone Atox1 in ECs plays an essential role to sense Cu to accelerate wound angiogenesis and healing.« less

Factors differentiating callous-unemotional children with and without conduct problems.

PubMed

Wall, Tina D; Frick, Paul J; Fanti, Kostas A; Kimonis, Eva R; Lordos, Alexandros

2016-08-01

Callous-unemotional (CU) traits are a risk factor for a severe, aggressive, and persistent pattern of conduct problems (CP). This study investigated characteristics that might differentiate children with elevated CU traits with and without CP in an effort to identify factors that may reduce the risk for CP in children with limited prosocial emotions. Utilizing a sample of 1,366 children from Cyprus, five groups were identified for further study based on latent profile analysis: low-risk (67.2%), high-CP/low-CU (7.9%), high-CU (9.4%), moderate-CP/CU (8.4%), and high-CP/CU (7.2%). The identified groups were compared on behavioral and social measures. There were significant main effects of group for: impulsivity and executive functioning; parenting; and connectedness to school. The high-CU group had significantly lower hyperactivity-impulsivity and executive functioning deficits, significantly higher self-regulation, and their mothers reported more maternal involvement and positive parenting than those in the high-CP/CU group. Also, the high-CU group showed more school connectedness than those in the high-CP/CU group. These findings highlight several factors in the child and in his or her social environment that are associated with CU traits in the absence of serious CP and that may suggest targets for intervention for youth who may lack prosocial emotions. © 2016 Association for Child and Adolescent Mental Health.

Endothelial Antioxidant-1: A key mediator of Copper-dependent wound healing in vivo

DOE PAGES

Das, Archita; Sudhahar, Varadarajan; Chen, Gin -Fu; ...

2016-09-26

Here, Copper (Cu), an essential nutrient, promotes wound healing, however, target of Cu action and underlying mechanisms remains elusive. Cu chaperone Antioxidant-1 (Atox1) in the cytosol supplies Cu to the secretory enzymes such as lysyl oxidase (LOX) while Atox1 in the nucleus functions as a Cu-dependent transcription factor. Using cutaneous wound healing model, here we show that Cu content (by X-ray Fluorescence Microscopy) and nuclear Atox1 are increased after wounding, and that wound healing with and without Cu treatment is impaired in Atox1 -/ - mice. Experiments using endothelial cell (EC)-specific Atox1 -/ - mice and gene transfer of nuclear-targetmore » Atox1 in Atox1 -/ - mice reveal that Atox1 in ECs as well as transcription factor function of Atox1 are required for wound healing. Mechanistically, Atox1 -/ - mice show reduced Atox1 target proteins such as p47phox NADPH oxidase and cyclin D1 as well as extracellular matrix Cu enzyme LOX activity in wound tissues. This in turn results in reducing O 2 - production in ECs, NFkB activity, cell proliferation and collagen formation, thereby inhibiting angiogenesis, macrophage recruitment and extracellular matrix maturation. Our findings suggest that Cu-dependent transcription factor/Cu chaperone Atox1 in ECs plays an essential role to sense Cu to accelerate wound angiogenesis and healing.« less

Bombesin functionalized 64Cu-copper sulfide nanoparticles for targeted imaging of orthotopic prostate cancer.

PubMed

Cai, Huawei; Xie, Fang; Mulgaonkar, Aditi; Chen, Lihong; Sun, Xiankai; Hsieh, Jer-Tsong; Peng, Fangyu; Tian, Rong; Li, Lin; Wu, Changqiang; Ai, Hua

2018-05-22

To synthesize and evaluate the imaging potential of Bom-PEG-[ 64 Cu]CuS nanoparticles (NPs) in orothotopic prostate tumor. [ 64 Cu]CuS NPs were synthesized in aqueous solution by 64 CuCl 2 and Na 2 S reaction. Then PEG linker with or without bombesin peptide were conjugated to the surface of [ 64 Cu]CuS NPs to produce Bom-PEG-[ 64 Cu]CuS and PEG-[ 64 Cu]CuS NPs. These two kinds of NPs were used for testing specific uptake in prostate cancer cells in vitro and imaging of orthotopic prostate tumor in vivo. Bom-PEG-[ 64 Cu]CuS and PEG-[ 64 Cu]CuS NPs were successfully synthesized with core diameter of approximately 5 nm. Radioactive cellular uptake revealed that Bom-PEG-[ 64 Cu]CuS was able to specifically bind to prostate cancer cells, and the microPET-CT imaging indicated clear visualization of orthotopic prostate tumors. Radiolabeled Bom-PEG-[ 64 Cu]CuS NPs have potential as an ideal agent for orthotopic prostate tumor imaging by microPET-CT.

Copper Ion Detection in Drinking Water via a Fabric Nanocomposite Sensor

NASA Astrophysics Data System (ADS)

Yu, Guoqiang

Excessive Cu(II) ions in drinking water are always a big threat to people's health. In this work, we developed a flexible amperometric sensor by a simple dip-coating method, which was able to rapidly, sensitively, and selectively detect the Cu(II) ions in the range of 0.65 to 39 ppm in real time. The prepared Cu(II) sensor consisted of three layers that were electrospun nylon-6 nanofibers, multiwalled carbon nanotubes (MWCNTs), and 2,2':5',2''-terthiophene molecules, respectively. When a voltage was applied to the Cu(II) sensor, the current was obviously impeded in the presence of Cu(II) ions. Interfering metal ions, including Cd(II), Fe(II), Pb(II), Hg(II), and Ag(I) ions, had almost no influence on the responsiveness of the Cu(II) sensor.

Comparative effects of graphene and graphene oxide on copper toxicity to Daphnia magna: Role of surface oxygenic functional groups.

PubMed

Liu, Yingying; Fan, Wenhong; Xu, Zhizhen; Peng, Weihua; Luo, Shenglian

2018-05-01

Although the risk of graphene materials to aquatic organisms has drawn wide attention, the combined effects of graphene materials with other contaminants such as toxic metals, which may bring about more serious effects than graphene materials alone, have seldom been explored. Herein, the effects of graphene (GN) and graphene oxide (GO, an important oxidized derivative of graphene) on copper (Cu) toxicity to Daphnia magna were systematically investigated. The results indicated that GN remarkably increased the Cu accumulation in D. magna and enhanced the oxidative stress injury caused by Cu, whereas did not significantly alter D. magna acute mortality within the tested Cu concentrations (0-200 μg L -1 ). On the contrary, GO significantly decreased the Cu accumulation in D. magna and alleviated the oxidative stress injury caused by Cu. Meanwhile, the presence of GO significantly reduced the mortality of D. magna when Cu concentration exceeded 50 μg L -1 . The different effects of GN and GO on Cu toxicity were possibly dependent on the action of surface oxygenic functional group. Because of the introduction of surface oxygenic functional groups, the adsorption ability to metal ions, stability in water and interaction mode with organisms of GO are quite different from that of GN, causing different effects on Cu toxicity. This study provides important information on the bioavailability and toxicity of heavy metals as affected by graphene materials in natural water. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Functionality of Surface Hydroxy Groups on the Selectivity and Activity of Carbon Dioxide Reduction over Cuprous Oxide in Aqueous Solutions.

PubMed

Yang, Piaoping; Zhao, Zhi-Jian; Chang, Xiaoxia; Mu, Rentao; Zha, Shenjun; Zhang, Gong; Gong, Jinlong

2018-06-25

Carbon dioxide (CO 2 ) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu 2 O) is a promising catalyst for CO 2 reduction as it can convert CO 2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu 2 O remains under debate because of the complex surface structure of Cu 2 O under reducing conditions, leading to limited guidance in designing improved Cu 2 O catalysts. This paper describes the functionality of surface-bonded hydroxy groups on partially reduced Cu 2 O(111) for the CO 2 reduction reaction (CO 2 RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO 2 RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO 2 RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination-unsaturated Cu (Cu CUS ) sites stabilizes surface-adsorbed COOH*, which is a key intermediate during the CO 2 RR. Moreover, the CO 2 RR was evaluated over Cu 2 O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu 2 O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO 2 RR and suppress the HER. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembled monolayer structures of hexadecylamine on Cu surfaces: density-functional theory.

PubMed

Liu, Shih-Hsien; Balankura, Tonnam; Fichthorn, Kristen A

2016-12-07

We used dispersion-corrected density-functional theory to probe possible structures for adsorbed layers of hexadecylamine (HDA) on Cu(100) and Cu(111). HDA forms self-assembled layers on these surfaces, analogous to alkanethiols on various metal surfaces, and it binds by donating electrons in the amine group to the Cu surface atoms, consistent with experiment. van der Waals interactions between the alkyl tails of HDA molecules are stronger than the interaction between the amine group and the Cu surfaces. Strong HDA-tail interactions lead to coverage-dependent tilting of the HDA layers, such that the tilt angle is larger for lower coverages. At full monolayer coverage, the energetically preferred binding configuration for HDA on Cu(100) is a (5 × 3) pattern - although we cannot rule out incommensurate structures - while the pattern is preferred on Cu(111). A major motivation for this study is to understand the experimentally observed capability of HDA as a capping agent for producing {100}-faceted Cu nanocrystals. Consistent with experiment, we find that HDA binds more strongly to Cu(100) than to Cu(111). This strong binding stems from the capability of HDA to form more densely packed layers on Cu(100), which leads to stronger HDA-tail interactions, as well as the stronger binding of the amine group to Cu(100). We estimate the surface energies of HDA-covered Cu(100) and Cu(111) surfaces and find that these surfaces are nearly isoenergetic. By drawing analogies to previous theoretical work, it seems likely that HDA-covered Cu nanocrystals could have kinetic shapes that primarily express {100} facets, as is seen experimentally.

Systematic study of azimuthal anisotropy in Cu + Cu and Au + Au collisions at √{sNN}=62.4 and 200 GeV

NASA Astrophysics Data System (ADS)

Adare, A.; Afanasiev, S.; Aidala, C.; Ajitanand, N. N.; Akiba, Y.; Al-Bataineh, H.; Al-Jamel, A.; Alexander, J.; Aoki, K.; Aphecetche, L.; Armendariz, R.; Aronson, S. H.; Asai, J.; Atomssa, E. T.; Averbeck, R.; Awes, T. C.; Azmoun, B.; Babintsev, V.; Baksay, G.; Baksay, L.; Baldisseri, A.; Barish, K. N.; Barnes, P. D.; Bassalleck, B.; Bathe, S.; Batsouli, S.; Baublis, V.; Bauer, F.; Bazilevsky, A.; Belikov, S.; Bennett, R.; Berdnikov, Y.; Bickley, A. A.; Bjorndal, M. T.; Boissevain, J. G.; Borel, H.; Boyle, K.; Brooks, M. L.; Brown, D. S.; Bucher, D.; Buesching, H.; Bumazhnov, V.; Bunce, G.; Burward-Hoy, J. M.; Butsyk, S.; Campbell, S.; Chai, J.-S.; Chang, B. S.; Charvet, J.-L.; Chernichenko, S.; Chi, C. Y.; Chiba, J.; Chiu, M.; Choi, I. J.; Chujo, T.; Chung, P.; Churyn, A.; Cianciolo, V.; Cleven, C. R.; Cobigo, Y.; Cole, B. A.; Comets, M. P.; Constantin, P.; Csanád, M.; Csörgő, T.; Dahms, T.; Das, K.; David, G.; Deaton, M. B.; Dehmelt, K.; Delagrange, H.; Denisov, A.; D'Enterria, D.; Deshpande, A.; Desmond, E. J.; Dietzsch, O.; Dion, A.; Donadelli, M.; Drachenberg, J. L.; Drapier, O.; Drees, A.; Dubey, A. K.; Durum, A.; Dzhordzhadze, V.; Efremenko, Y. V.; Egdemir, J.; Ellinghaus, F.; Emam, W. S.; Enokizono, A.; En'yo, H.; Espagnon, B.; Esumi, S.; Eyser, K. O.; Fields, D. E.; Finger, M.; Finger, M.; Fleuret, F.; Fokin, S. L.; Forestier, B.; Fraenkel, Z.; Frantz, J. E.; Franz, A.; Frawley, A. D.; Fujiwara, K.; Fukao, Y.; Fung, S.-Y.; Fusayasu, T.; Gadrat, S.; Garishvili, I.; Gastineau, F.; Germain, M.; Glenn, A.; Gong, H.; Gonin, M.; Gosset, J.; Goto, Y.; Granier de Cassagnac, R.; Grau, N.; Greene, S. V.; Grosse Perdekamp, M.; Gunji, T.; Gustafsson, H.-Å.; Hachiya, T.; Hadj Henni, A.; Haegemann, C.; Haggerty, J. S.; Hagiwara, M. N.; Hamagaki, H.; Han, R.; Harada, H.; Hartouni, E. P.; Haruna, K.; Harvey, M.; Haslum, E.; Hasuko, K.; Hayano, R.; He, X.; Heffner, M.; Hemmick, T. K.; Hester, T.; Heuser, J. M.; Hiejima, H.; Hill, J. C.; Hobbs, R.; Hohlmann, M.; Holmes, M.; Holzmann, W.; Homma, K.; Hong, B.; Horaguchi, T.; Hornback, D.; Huang, S.; Hur, M. G.; Ichihara, T.; Iinuma, H.; Imai, K.; Inaba, M.; Inoue, Y.; Isenhower, D.; Isenhower, L.; Ishihara, M.; Isobe, T.; Issah, M.; Isupov, A.; Jacak, B. V.; Jia, J.; Jin, J.; Jinnouchi, O.; Johnson, B. M.; Joo, K. S.; Jouan, D.; Kajihara, F.; Kametani, S.; Kamihara, N.; Kamin, J.; Kaneta, M.; Kang, J. H.; Kanou, H.; Kawagishi, T.; Kawall, D.; Kazantsev, A. V.; Kelly, S.; Khanzadeev, A.; Kikuchi, J.; Kim, D. H.; Kim, D. J.; Kim, E.; Kim, Y.-S.; Kinney, E.; Kiss, Á.; Kistenev, E.; Kiyomichi, A.; Klay, J.; Klein-Boesing, C.; Kochenda, L.; Kochetkov, V.; Komkov, B.; Konno, M.; Kotchetkov, D.; Kozlov, A.; Král, A.; Kravitz, A.; Kroon, P. J.; Kubart, J.; Kunde, G. J.; Kurihara, N.; Kurita, K.; Kweon, M. J.; Kwon, Y.; Kyle, G. S.; Lacey, R.; Lai, Y. S.; Lajoie, J. G.; Lebedev, A.; Le Bornec, Y.; Leckey, S.; Lee, D. M.; Lee, M. K.; Lee, T.; Leitch, M. J.; Leite, M. A. L.; Lenzi, B.; Li, X.; Li, X. H.; Lim, H.; Liška, T.; Litvinenko, A.; Liu, M. X.; Love, B.; Lynch, D.; Maguire, C. F.; Makdisi, Y. I.; Malakhov, A.; Malik, M. D.; Manko, V. I.; Mao, Y.; Mašek, L.; Masui, H.; Matathias, F.; McCain, M. C.; McCumber, M.; McGaughey, P. L.; Miake, Y.; Mikeš, P.; Miki, K.; Miller, T. E.; Milov, A.; Mioduszewski, S.; Mishra, G. C.; Mishra, M.; Mitchell, J. T.; Mitrovski, M.; Morreale, A.; Morrison, D. P.; Moss, J. M.; Moukhanova, T. V.; Mukhopadhyay, D.; Murata, J.; Nagamiya, S.; Nagata, Y.; Nagle, J. L.; Naglis, M.; Nakagawa, I.; Nakamiya, Y.; Nakamura, T.; Nakano, K.; Newby, J.; Nguyen, M.; Norman, B. E.; Nouicer, R.; Nyanin, A. S.; Nystrand, J.; O'Brien, E.; Oda, S. X.; Ogilvie, C. A.; Ohnishi, H.; Ojha, I. D.; Oka, M.; Okada, K.; Omiwade, O. O.; Oskarsson, A.; Otterlund, I.; Ouchida, M.; Ozawa, K.; Pak, R.; Pal, D.; Palounek, A. P. T.; Pantuev, V.; Papavassiliou, V.; Park, J.; Park, W. J.; Pate, S. F.; Pei, H.; Peng, J.-C.; Pereira, H.; Peresedov, V.; Peressounko, D. Yu.; Pinkenburg, C.; Pisani, R. P.; Purschke, M. L.; Purwar, A. K.; Qu, H.; Rak, J.; Rakotozafindrabe, A.; Ravinovich, I.; Read, K. F.; Rembeczki, S.; Reuter, M.; Reygers, K.; Riabov, V.; Riabov, Y.; Roche, G.; Romana, A.; Rosati, M.; Rosendahl, S. S. E.; Rosnet, P.; Rukoyatkin, P.; Rykov, V. L.; Ryu, S. S.; Sahlmueller, B.; Saito, N.; Sakaguchi, T.; Sakai, S.; Sakata, H.; Samsonov, V.; Sato, H. D.; Sato, S.; Sawada, S.; Seele, J.; Seidl, R.; Semenov, V.; Seto, R.; Sharma, D.; Shea, T. K.; Shein, I.; Shevel, A.; Shibata, T.-A.; Shigaki, K.; Shimomura, M.; Shohjoh, T.; Shoji, K.; Sickles, A.; Silva, C. L.; Silvermyr, D.; Silvestre, C.; Sim, K. S.; Singh, C. P.; Singh, V.; Skutnik, S.; Slunečka, M.; Smith, W. C.; Soldatov, A.; Soltz, R. A.; Sondheim, W. E.; Sorensen, S. P.; Sourikova, I. V.; Staley, F.; Stankus, P. W.; Stenlund, E.; Stepanov, M.; Ster, A.; Stoll, S. P.; Sugitate, T.; Suire, C.; Sullivan, J. P.; Sziklai, J.; Tabaru, T.; Takagi, S.; Takagui, E. M.; Taketani, A.; Tanaka, K. H.; Tanaka, Y.; Tanida, K.; Tannenbaum, M. J.; Taranenko, A.; Tarján, P.; Thomas, T. L.; Todoroki, T.; Togawa, M.; Toia, A.; Tojo, J.; Tomášek, L.; Torii, H.; Towell, R. S.; Tram, V.-N.; Tserruya, I.; Tsuchimoto, Y.; Tuli, S. K.; Tydesjö, H.; Tyurin, N.; Vale, C.; Valle, H.; van Hecke, H. W.; Velkovska, J.; Vértesi, R.; Vinogradov, A. A.; Virius, M.; Vrba, V.; Vznuzdaev, E.; Wagner, M.; Walker, D.; Wang, X. R.; Watanabe, Y.; Wessels, J.; White, S. N.; Willis, N.; Winter, D.; Woody, C. L.; Wysocki, M.; Xie, W.; Yamaguchi, Y. L.; Yanovich, A.; Yasin, Z.; Ying, J.; Yokkaichi, S.; Young, G. R.; Younus, I.; Yushmanov, I. E.; Zajc, W. A.; Zaudtke, O.; Zhang, C.; Zhou, S.; Zimányi, J.; Zolin, L.; Phenix Collaboration

2015-09-01

We have studied the dependence of azimuthal anisotropy v2 for inclusive and identified charged hadrons in Au +Au and Cu +Cu collisions on collision energy, species, and centrality. The values of v2 as a function of transverse momentum pT and centrality in Au +Au collisions at √{s NN}=200 and 62.4 GeV are the same within uncertainties. However, in Cu +Cu collisions we observe a decrease in v2 values as the collision energy is reduced from 200 to 62.4 GeV. The decrease is larger in the more peripheral collisions. By examining both Au +Au and Cu +Cu collisions we find that v2 depends both on eccentricity and the number of participants, Npart. We observe that v2 divided by eccentricity (ɛ ) monotonically increases with Npart and scales as Npart1 /3. The Cu +Cu data at 62.4 GeV falls below the other scaled v2 data. For identified hadrons, v2 divided by the number of constituent quarks nq is independent of hadron species as a function of transverse kinetic energy K ET=mT-m between 0.1

Region segmentation and contextual cuing in visual search.

PubMed

Conci, Markus; von Mühlenen, Adrian

2009-10-01

Contextual information provides an important source for behavioral orienting. For instance, in the contextual-cuing paradigm, repetitions of the spatial layout of elements in a search display can guide attention to the target location. The present study explored how this contextual-cuing effect is influenced by the grouping of search elements. In Experiment 1, four nontarget items could be arranged collinearly to form an imaginary square. The presence of such a square eliminated the contextual-cuing effect, despite the fact that the square's location still had a predictive value for the target location. Three follow-up experiments demonstrated that other types of grouping abolished contextual cuing in a similar way and that the mere presence of a task-irrelevant singleton had only a diminishing effect (by half) on contextual cuing. These findings suggest that a segmented, salient region can interfere with contextual cuing, reducing its predictive impact on search.

Antibacterial effect of copper-bearing titanium alloy (Ti-Cu) against Streptococcus mutans and Porphyromonas gingivalis

NASA Astrophysics Data System (ADS)

Liu, Rui; Memarzadeh, Kaveh; Chang, Bei; Zhang, Yumei; Ma, Zheng; Allaker, Robert P.; Ren, Ling; Yang, Ke

2016-07-01

Formation of bacterial biofilms on dental implant material surfaces (titanium) may lead to the development of peri-implant diseases influencing the long term success of dental implants. In this study, a novel Cu-bearing titanium alloy (Ti-Cu) was designed and fabricated in order to efficiently kill bacteria and discourage formation of biofilms, and then inhibit bacterial infection and prevent implant failure, in comparison with pure Ti. Results from biofilm based gene expression studies, biofilm growth observation, bacterial viability measurements and morphological examination of bacteria, revealed antimicrobial/antibiofilm activities of Ti-Cu alloy against the oral specific bacterial species, Streptococcus mutans and Porphyromonas gingivalis. Proliferation and adhesion assays with mesenchymal stem cells, and measurement of the mean daily amount of Cu ion release demonstrated Ti-Cu alloy to be biocompatible. In conclusion, Ti-Cu alloy is a promising dental implant material with antimicrobial/antibiofilm activities and acceptable biocompatibility.

Influences of film thickness on the structural, electrical and optical properties of CuAlO2 thin films

NASA Astrophysics Data System (ADS)

Dong, Guobo; Zhang, Ming; Wang, Mei; Li, Yingzi; Gao, Fangyuan; Yan, Hui; Diao, Xungang

2014-07-01

CuAlO2 films with different thickness were prepared by the radio frequency magnetron sputtering technique. The structural, electrical and optical properties of CuAlO2 were studied by X-ray diffraction, atomic force microscope, UV-Vis double-beam spectrophotometer and Hall measurements. The results indicate that the single phase hexagonal CuAlO2 is formed and the average grain size of CuAlO2 films increases with increasing film thickness. The results also exhibit that the lowering of bandgap and the increase of electrical conductivity of CuAlO2 films with the increase of their thickness, which are attributed to the improvement of the grain size and the anisotropic electrical property. According to the electrical and optical properties, the biggest figure of merit is achieved for the CuAlO2 film with the appropriate thickness of 165 nm.

Ammonia Vapor-Assisted Synthesis of Cu(OH)2 and CuO Nanostructures: Anionic (Cl-, NO3 -, SO4 2-) Influence on the Product Morphology

NASA Astrophysics Data System (ADS)

Mansournia, Mohammadreza; Arbabi, Akram

2017-01-01

Shape control of inorganic nanostructures generally requires using surfactants or ligands to passivate certain crystallographic planes. This paper describes a novel additive-free synthesis of cupric oxide nanostructures with different morphologies from the aqueous solutions of copper(II) with Cl-, NO3 -, and SO4 2- as counter ions. Through a one-step approach, CuO nanoleaves, nanoparticles and flower-like microspheres were directly synthesized at 80°C upon exposure to ammonia vapor using a cupric solution as a single precursor. Furthermore, during a two-step process, Cu(OH)2 nanofibers and nanorods were prepared under an ammonia atmosphere, then converted to CuO nanostructures with morphology preservation by heat treatment in air. The as-prepared Cu(OH)2 and CuO nanostructures are characterized using x-ray diffraction, scanning electron microscopy and Fourier transformation infrared spectroscopy techniques.

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities. Electronic supplementary information (ESI) available: Synthesis and TEM images of pure ZnO nanocrystals. Photocatalytic testing procedures and degradation curves. SEM and TEM images, SAED pattern and EDS spectra and maps of parts of Cu-ZnO hybrid samples. A schematic image of coincident lattice matching between Cu and ZnO. STEM-EDS elemental maps and XRD pattern of the Cu@CuNi-ZnO sample. Comparative synthetic parameters. See DOI: 10.1039/c6nr02055k

Simulating contrast inversion in atomic force microscopy imaging with real-space pseudopotentials

NASA Astrophysics Data System (ADS)

Lee, Alex J.; Sakai, Yuki; Chelikowsky, James R.

2017-02-01

Atomic force microscopy (AFM) measurements have reported contrast inversions for systems such as Cu2N and graphene that can hamper image interpretation and characterization. Here, we apply a simulation method based on ab initio real-space pseudopotentials to gain an understanding of the tip-sample interactions that influence the inversion. We find that chemically reactive tips induce an attractive binding force that results in the contrast inversion. We find that the inversion is tip height dependent and not observed when using less reactive CO-functionalized tips.

Removal of Cu(II) metal ions from aqueous solution by amine functionalized magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Kothavale, V. P.; Karade, V. C.; Waifalkar, P. P.; Sahoo, Subasa C.; Patil, P. S.; Patil, P. B.

2018-04-01

The adsorption behavior of Cu(II) metal cations was investigated on the amine functionalized magnetic nanoparticles (MNPs). TheMNPs were synthesized by thesolvothermal method and functionalized with (3-Aminopropyl)triethoxysilane (APTES). MNPs were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and vibrating sample magnetometer (VSM). The MNPs have pure magnetite phase with particle size around 10-12 nm. MNPs exhibits superparamagnetic behavior with asaturation magnetization of 68 emu/g. The maximum 38 % removal efficiency was obtained for Cu(II) metal ions from the aqueous solution.

Biodynamics of copper oxide nanoparticles and copper ions in an oligochaete: Part I: relative importance of water and sediment as exposure routes

USGS Publications Warehouse

Ramskov, Tina; Thit, Amalie; Croteau, Marie-Noele; Selck, Henriette

2015-01-01

Copper oxide (CuO) nanoparticles (NPs) are widely used, and likely released into the aquatic environment. Both aqueous (i.e., dissolved Cu) and particulate Cu can be taken up by organisms. However, how exposure routes influence the bioavailability and subsequent toxicity of Cu remains largely unknown. Here, we assess the importance of exposure routes (water and sediment) and Cu forms (aqueous and nanoparticulate) on Cu bioavailability and toxicity to the freshwater oligochaete, Lumbriculus variegatus, a head-down deposit-feeder. We characterize the bioaccumulation dynamics of Cu in L. variegatus across a range of exposure concentrations, covering both realistic and worst-case levels of Cu contamination in the environment. Both aqueous Cu (Cu-Aq; administered as Cu(NO3)2) and nanoparticulate Cu (CuO NPs), whether dispersed in artificial moderately hard freshwater or mixed into sediment, were weakly accumulated by L. variegatus. Once incorporated into tissues, Cu elimination was negligible, i.e., elimination rate constants were in general not different from zero for either exposure route or either Cu form. Toxicity was only observed after waterborne exposure to Cu-Aq at very high concentration (305 µgL-1), where all worms died. There was no relationship between exposure route, Cu form or Cu exposure concentration on either worm survival or growth. Slow feeding rates and low Cu assimilation efficiency (approximately 30%) characterized the uptake of Cu from the sediment for both Cu forms. In nature, L. variegatus is potentially exposed to Cu via both water and sediment. However, sediment progressively becomes the predominant exposure route for Cu in L. variegatus as Cu partitioning to sediment increases.

Influence of surface oxygenated groups on the formation of active Cu species and the catalytic activity of Cu/AC catalyst for the synthesis of dimethyl carbonate

NASA Astrophysics Data System (ADS)

Zhang, Guoqiang; Li, Zhong; Zheng, Huayan; Hao, Zhiqiang; Wang, Xia; Wang, Jiajun

2016-12-01

Activated carbon (AC) supported Cu catalysts are employed to study the influence of surface oxygenated groups on the formation of active Cu species and the catalytic activity of Cu/AC catalyst for oxidative carbonylation of methanol to dimethyl carbonate (DMC). The AC supports are thermal treated under different temperatures in order to adjust the levels of surface oxygenated groups. The AC supports are characterized by BET, TPD-MS and XRD, and the Cu/AC catalysts are characterized by BET, XRD, TEM, XPS, AAS, CH3OH-TPD and N2O chemisorption. The results show that as the treatment temperature is below 800 °C, the BET surface area of the corresponding AC supports are nearly unchanged and close to that of the original AC (1529.6 m2/g). But as the thermal treatment temperature is elevated from 1000 to 1600 °C, the BET surface area of AC supports gradually decreases from 1407.6 to 972.2 m2/g. After loading of Cu, the BET surface area of copper catalysts is in the range of 834.4 to 1545.3 m2/g, which is slightly less than that of the respective supports. When AC is thermal treated at 400 and 600 °C, the unstable carboxylic acid and anhydrides groups are selectively removed, which has weakened the mobility and agglomeration of Cu species during the calcination process, and thus improve the Cu species dispersion over AC support. But as the treatment temperature is elevated from 600 °C to 1200 °C, the Cu species dispersion begins to decline suggesting further removal of stable surface oxygenated groups is unfavorable for Cu species dispersion. Moreover, higher thermal treatment temperature (above 1200 °C) promotes the graphitization degree of AC and leds to the decrease of Cu loading on AC support. Meanwhile, the removal of surface oxygenated groups by thermal treatment is conducive to the formation of more π-sites, and thus promote the reduction of Cu2+ to Cu+ and Cu0 as active centers. The specific surface area of (Cu+ + Cu0) is improved by thermal treatment of AC, however, the space time yield of DMC on unit specific surface area of (Cu+ + Cu0) is in the range of 23.1-49.1 mg h-1 m-2, which is much less than that (77.6 mg h-1 m-2) of the original catalyst. The possible reason is that the removal of surface oxygenated groups results in AC support transforms from hydrophilicity to hydrophobicity, which is detrimental for the adsorption of CH3OH resulting in the decreased local concentration of CH3OH on active Cu species.

Examining the specific contributions of individual Arabidopsis metallothioneins to copper distribution and metal tolerance.

PubMed

Guo, Woei-Jiun; Meetam, Metha; Goldsbrough, Peter B

2008-04-01

Metallothioneins (MTs) are small cysteine-rich proteins found in various eukaryotes. Plant MTs are classified into four types based on the arrangement of cysteine residues. To determine whether all four types of plant MTs function as metal chelators, six Arabidopsis (Arabidopsis thaliana) MTs (MT1a, MT2a, MT2b, MT3, MT4a, and MT4b) were expressed in the copper (Cu)- and zinc (Zn)-sensitive yeast mutants, Deltacup1 and Deltazrc1 Deltacot1, respectively. All four types of Arabidopsis MTs provided similar levels of Cu tolerance and accumulation to the Deltacup1 mutant. The type-4 MTs (MT4a and MT4b) conferred greater Zn tolerance and higher accumulation of Zn than other MTs to the Deltazrc1 Deltacot1 mutant. To examine the functions of MTs in plants, we studied Arabidopsis plants that lack MT1a and MT2b, two MTs that are expressed in phloem. The lack of MT1a, but not MT2b, led to a 30% decrease in Cu accumulation in roots of plants exposed to 30 mum CuSO(4). Ectopic expression of MT1a RNA in the mt1a-2 mt2b-1 mutant restored Cu accumulation in roots. The mt1a-2 mt2b-1 mutant had normal metal tolerance. However, when MT deficiency was combined with phytochelatin deficiency, growth of the mt1a-2 mt2b-1 cad1-3 triple mutant was more sensitive to Cu and cadmium compared to the cad1-3 mutant. Together these results provide direct evidence for functional contributions of MTs to plant metal homeostasis. MT1a, in particular, plays a role in Cu homeostasis in the roots under elevated Cu. Moreover, MTs and phytochelatins function cooperatively to protect plants from Cu and cadmium toxicity.

The influence of different locations of sputter guns on the morphological and structural properties of Cu-In-Ga precursors and Cu(In,Ga)Se2 thin films

NASA Astrophysics Data System (ADS)

Wang, J.; Zhu, J.; He, Y. X.

2014-01-01

The influence of two different locations of sputter guns on the morphological and structural properties of Cu-In-Ga precursors and Cu(In,Ga)Se2 (CIGS) thin films was investigated. All the precursors contained cauliflower-like nodules, whereas smaller subnodules were observed on the background. All the precursors revealed apparent three-layered structures, and voids were observed at the CIGS/SLG interface of Sets 1 and 2 films rather than Set 3 film. EDS results indicated that all CIGS thin films were Cu-deficient. Based on the grazing incidence X-ray diffraction (GIXRD) patterns, as-selenized films showed peaks corresponding to the chalcopyrite-type CIGS structure. Depth-resolved Raman spectra showed the formation of a dominant CIGS phase inside the films for all the as-selenized samples investigated, and of an ordered vacancy compound (OVC) phase like Cu(In,Ga)3Se5 or Cu(In,Ga)2Se3.5 at the surface and/or CIGS/SLG interface region of Sets 2 and 3 films. No evidence was obtained on the presence of an OVC phase in Set 1 CIGS film, which may be speculated that long-time annealing is contributed to suppress the growth of OVC phases. The results of the present work suggest that the metallic precursors deposited with the upright-location sputter gun might be more appropriate to prepare CIGS thin films than those sputtered with the titled-location gun.

Involuntary orienting of attention to a sound desynchronizes the occipital alpha rhythm and improves visual perception.

PubMed

Feng, Wenfeng; Störmer, Viola S; Martinez, Antigona; McDonald, John J; Hillyard, Steven A

2017-04-15

Directing attention voluntarily to the location of a visual target results in an amplitude reduction (desynchronization) of the occipital alpha rhythm (8-14Hz), which is predictive of improved perceptual processing of the target. Here we investigated whether modulations of the occipital alpha rhythm triggered by the involuntary orienting of attention to a salient but spatially non-predictive sound would similarly influence perception of a subsequent visual target. Target discrimination was more accurate when a sound preceded the target at the same location (validly cued trials) than when the sound was on the side opposite to the target (invalidly cued trials). This behavioral effect was accompanied by a sound-induced desynchronization of the alpha rhythm over the lateral occipital scalp. The magnitude of alpha desynchronization over the hemisphere contralateral to the sound predicted correct discriminations of validly cued targets but not of invalidly cued targets. These results support the conclusion that cue-induced alpha desynchronization over the occipital cortex is a manifestation of a general priming mechanism that improves visual processing and that this mechanism can be activated either by the voluntary or involuntary orienting of attention. Further, the observed pattern of alpha modulations preceding correct and incorrect discriminations of valid and invalid targets suggests that involuntary orienting to the non-predictive sound has a rapid and purely facilitatory influence on processing targets on the cued side, with no inhibitory influence on targets on the opposite side. Copyright © 2017 Elsevier Inc. All rights reserved.

Bioaccumulation and toxicity of CuO nanoparticles by a freshwater invertebrate after waterborne and dietborne exposures

USGS Publications Warehouse

Croteau, Marie-Noele; Misra, Superb K.; Luoma, Samuel N.; Valsami-Jones, Eugenia

2014-01-01

The incidental ingestion of engineered nanoparticles (NPs) can be an important route of uptake for aquatic organisms. Yet, knowledge of dietary bioavailability and toxicity of NPs is scarce. Here we used isotopically modified copper oxide (65CuO) NPs to characterize the processes governing their bioaccumulation in a freshwater snail after waterborne and dietborne exposures. Lymnaea stagnalis efficiently accumulated 65Cu after aqueous and dietary exposures to 65CuO NPs. Cu assimilation efficiency and feeding rates averaged 83% and 0.61 g g–1 d–1 at low exposure concentrations (–1), and declined by nearly 50% above this concentration. We estimated that 80–90% of the bioaccumulated 65Cu concentration in L. stagnalis originated from the 65CuO NPs, suggesting that dissolution had a negligible influence on Cu uptake from the NPs under our experimental conditions. The physiological loss of 65Cu incorporated into tissues after exposures to 65CuO NPs was rapid over the first days of depuration and not detectable thereafter. As a result, large Cu body concentrations are expected in L. stagnalis after exposure to CuO NPs. To the degree that there is a link between bioaccumulation and toxicity, dietborne exposures to CuO NPs are likely to elicit adverse effects more readily than waterborne exposures.

Influences of TiO2 phase structures on the structures and photocatalytic hydrogen production of CuOx/TiO2 photocatalysts

NASA Astrophysics Data System (ADS)

Liu, Yuanxu; Wang, Zhonglei; Huang, Weixin

2016-12-01

CuOx/TiO2 photocatalysts employing TiO2 with different phase structures as well as P25 as supports were prepared, and their structures and activity for photocatalytic H2 production in methanol/water solution under simulated solar light were comparatively studied. Structural characterization results demonstrated that the TiO2 phase structure strongly affects the CuOx-TiO2 interaction and copper species in various CuOx/TiO2 photocatalysts. The Cu2O-rutile TiO2 interaction is much stronger than the Cu2O-anatase TiO2 interaction, facilitates the interfacial charge transfer process within the Cu2O-rutile TiO2 heterojunction but disables supported Cu2O to catalyze the hole-participated methanol oxidation. The Cu2O-anatase TiO2 heterojunction with the appropriate Cu2O-anatase TiO2 interaction and thus the balancing efficiencies between the interfacial charge transfer process and hole-participated methanol oxidation is most photocatalytic active, and CuOx/P25 with the largest population of Cu2O-anatase TiO2 heterojunction exhibits the highest photocatalytic H2 production. These results provide novel insights in the applied surface science of CuOx/TiO2 photocatalysts.

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part I. Microstructural Characterization of Rapidly Solidified Solders

NASA Astrophysics Data System (ADS)

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.; Handwerker, Carol A.

2016-12-01

Particles of Cu x Al y in Sn-Cu-Al solders have previously been shown to nucleate the Cu6Sn5 phase during solidification. In this study, the number and size of Cu6Sn5 nucleation sites were controlled through the particle size refinement of Cu x Al y via rapid solidification processing and controlled cooling in a differential scanning calorimeter. Cooling rates spanning eight orders of magnitude were used to refine the average Cu x Al y and Cu6Sn5 particle sizes down to submicron ranges. The average particle sizes, particle size distributions, and morphologies in the microstructures were analyzed as a function of alloy composition and cooling rate. Deep etching of the samples revealed the three-dimensional microstructures and illuminated the epitaxial and morphological relationships between the Cu x Al y and Cu6Sn5 phases. Transitions in the Cu6Sn5 particle morphologies from faceted rods to nonfaceted, equiaxed particles were observed as a function of both cooling rate and composition. Initial solidification cooling rates within the range of 103 to 104 °C/s were found to be optimal for realizing particle size refinement and maintaining the Cu x Al y /Cu6Sn5 nucleant relationship. In addition, little evidence of the formation or decomposition of the ternary- β phase in the solidified alloys was noted. Solidification pathways omitting the formation of the ternary- β phase agreed well with observed room temperature microstructures.

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part I. Microstructural Characterization of Rapidly Solidified Solders

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

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.

Particles of Cu x Al y in Sn-Cu-Al solders have previously been shown to nucleate the Cu 6Sn 5 phase during solidification. In this study, the number and size of Cu 6Sn 5 nucleation sites were controlled through the particle size refinement of Cu x Al y via rapid solidification processing and controlled cooling in a differential scanning calorimeter. Cooling rates spanning eight orders of magnitude were used to refine the average Cu x Al y and Cu 6Sn 5 particle sizes down to submicron ranges. The average particle sizes, particle size distributions, and morphologies in the microstructures were analyzedmore » as a function of alloy composition and cooling rate. Deep etching of the samples revealed the three-dimensional microstructures and illuminated the epitaxial and morphological relationships between the Cu x Al y and Cu 6Sn 5 phases. Transitions in the Cu 6Sn 5 particle morphologies from faceted rods to nonfaceted, equiaxed particles were observed as a function of both cooling rate and composition. Initial solidification cooling rates within the range of 10 3 to 10 4 °C/s were found to be optimal for realizing particle size refinement and maintaining the Cu x Al y /Cu 6Sn 5 nucleant relationship. In addition, little evidence of the formation or decomposition of the ternary-β phase in the solidified alloys was noted. As a result, solidification pathways omitting the formation of the ternary-β phase agreed well with observed room temperature microstructures.« less

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part I. Microstructural Characterization of Rapidly Solidified Solders

DOE PAGES

Reeve, Kathlene N.; Choquette, Stephanie M.; Anderson, Iver E.; ...

2016-10-06

Particles of Cu x Al y in Sn-Cu-Al solders have previously been shown to nucleate the Cu 6Sn 5 phase during solidification. In this study, the number and size of Cu 6Sn 5 nucleation sites were controlled through the particle size refinement of Cu x Al y via rapid solidification processing and controlled cooling in a differential scanning calorimeter. Cooling rates spanning eight orders of magnitude were used to refine the average Cu x Al y and Cu 6Sn 5 particle sizes down to submicron ranges. The average particle sizes, particle size distributions, and morphologies in the microstructures were analyzedmore » as a function of alloy composition and cooling rate. Deep etching of the samples revealed the three-dimensional microstructures and illuminated the epitaxial and morphological relationships between the Cu x Al y and Cu 6Sn 5 phases. Transitions in the Cu 6Sn 5 particle morphologies from faceted rods to nonfaceted, equiaxed particles were observed as a function of both cooling rate and composition. Initial solidification cooling rates within the range of 10 3 to 10 4 °C/s were found to be optimal for realizing particle size refinement and maintaining the Cu x Al y /Cu 6Sn 5 nucleant relationship. In addition, little evidence of the formation or decomposition of the ternary-β phase in the solidified alloys was noted. As a result, solidification pathways omitting the formation of the ternary-β phase agreed well with observed room temperature microstructures.« less

Predicting a quaternary tungsten oxide for sustainable photovoltaic application by density functional theory

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

Sarker, Pranab; Huda, Muhammad N., E-mail: huda@uta.edu; Al-Jassim, Mowafak M.

2015-12-07

A quaternary oxide, CuSnW{sub 2}O{sub 8} (CTTO), has been predicted by density functional theory (DFT) to be a suitable material for sustainable photovoltaic applications. CTTO possesses band gaps of 1.25 eV (indirect) and 1.37 eV (direct), which were evaluated using the hybrid functional (HSE06) as a post-DFT method. The hole mobility of CTTO was higher than that of silicon. Further, optical absorption calculations demonstrate that CTTO is a better absorber of sunlight than Cu{sub 2}ZnSnS{sub 4} and CuIn{sub x}Ga{sub 1−x}Se{sub 2} (x = 0.5). In addition, CTTO exhibits rigorous thermodynamic stability comparable to WO{sub 3}, as investigated by different thermodynamic approaches such as bondingmore » cohesion, fragmentation tendency, and chemical potential analysis. Chemical potential analysis further revealed that CTTO can be synthesized at flexible experimental growth conditions, although the co-existence of at least one secondary phase is likely. Finally, like other Cu-based compounds, the formation of Cu vacancies is highly probable, even at Cu-rich growth condition, which could introduce p-type activity in CTTO.« less

Impact of S fertilizers on pore-water Cu dynamics and transformation in a contaminated paddy soil with various flooding periods.

PubMed

Yang, Jianjun; Zhu, Shenhai; Zheng, Cuiqing; Sun, Lijuan; Liu, Jin; Shi, Jiyan

2015-04-09

Impact of S fertilization on Cu mobility and transformation in contaminated paddy soils has been little reported. In this study, we investigated the dynamics and transformation of dissolved and colloidal Cu in the pore water of a contaminated paddy soil after applying ammonium sulphate (AS) and sulfur coated urea (SCU) with various flooding periods (1, 7 and 60 days). Compared to the control soil, the AS-treated soil released more colloidal and dissolved Cu over the entire flooding period, while the SCU-treated soil had lower colloidal Cu after 7-day flooding but higher colloidal and dissolved Cu after 60-day flooding. Microscopic X-ray fluorescence (μ-XRF) analysis found a close relationship between Fe and Cu distribution on soil colloids after 60-day flooding, implying the formation of colloidal Fe/Cu sulphide coprecipitates. Cu K-edge X-ray absorption near-edge structure (XANES) spectroscopy directly revealed the transformation of outer-sphere complexed Cu(II) species to Cu(II) sulphide and reduced Cu2O in the colloids of S-treated soils after 60-day flooding. These results demonstrated the great influence of S fertilization on pore-water Cu mobility by forming Cu sulphide under flooding conditions, which facilitated our understanding and control of Cu loss in contaminated paddy soils under S fertilization. Copyright © 2015 Elsevier B.V. All rights reserved.

Impacts of human activity modes and climate on heavy metal "spread" in groundwater are biased.

PubMed

Chen, Ming; Qin, Xiaosheng; Zeng, Guangming; Li, Jian

2016-06-01

Groundwater quality deterioration has attracted world-wide concerns due to its importance for human water supply. Although more and more studies have shown that human activities and climate are changing the groundwater status, an investigation on how different groundwater heavy metals respond to human activity modes (e.g. mining, waste disposal, agriculture, sewage effluent and complex activity) in a varying climate has been lacking. Here, for each of six heavy metals (i.e. Fe, Zn, Mn, Pb, Cd and Cu) in groundwater, we use >330 data points together with mixed-effect models to indicate that (i) human activity modes significantly influence the Cu and Mn but not Zn, Fe, Pb and Cd levels, and (ii) annual mean temperature (AMT) only significantly influences Cu and Pb levels, while annual precipitation (AP) only significantly affects Fe, Cu and Mn levels. Given these differences, we suggest that the impacts of human activity modes and climate on heavy metal "spread" in groundwater are biased. Copyright © 2016 Elsevier Ltd. All rights reserved.

Subcellular metal imaging identifies dynamic sites of Cu accumulation in Chlamydomonas

DOE PAGES

Hong-Hermesdorf, Anne; Miethke, Marcus; Gallaher, Sean D.; ...

2014-10-26

Here we identified a Cu-accumulating structure with a dynamic role in intracellular Cu homeostasis. During Zn limitation, Chlamydomonas reinhardtii hyperaccumulates Cu, a process dependent on the nutritional Cu sensor CRR1, but it is functionally Cu deficient. Visualization of intracellular Cu revealed major Cu accumulation sites coincident with electron-dense structures that stained positive for low pH and polyphosphate, suggesting that they are lysosome-related organelles. Nano-secondary ion MS showed colocalization of Ca and Cu, and X-ray absorption spectroscopy was consistent with Cu + accumulation in an ordered structure. Zn resupply restored Cu homeostasis concomitant with reduced abundance of these structures. Cu isotopemore » labeling demonstrated that sequestered Cu + became bioavailable for the synthesis of plastocyanin, and transcriptome profiling indicated that mobilized Cu became visible to CRR1. Cu trafficking to intracellular accumulation sites may be a strategy for preventing protein mismetallation during Zn deficiency and enabling efficient cuproprotein metallation or remetallation upon Zn resupply.« less

Effects of copper-precursors on the catalytic activity of Cu/graphene catalysts for the selective catalytic oxidation of ammonia

NASA Astrophysics Data System (ADS)

Li, Jingying; Tang, Xiaolong; Yi, Honghong; Yu, Qingjun; Gao, Fengyu; Zhang, Runcao; Li, Chenlu; Chu, Chao

2017-08-01

Different copper-precursors were used to prepare Cu/graphene catalysts by an impregnation method. XRD, Raman spectra, TEM, BET, XPS, H2-TPR, NH3-TPD, DRIFTS and catalytic activity test were used to characterize and study the effect of precursors on the catalytic activity of Cu/graphene catalysts for NH3-SCO reaction. The large specific surface area of Cu/graphene catalysts and high dispersion of the metal particles on the graphene caused the well catalytic activity of NH3-SCO reaction. Compared to Cu/GE(AC), Cu/GE(N) showed better catalytic performance, and the complete NH3 removal efficiency was obtained at 250 °C with N2 selectivity of 85%. The copper-precursors had influence on the distribution of surface Cu species and further affected the catalytic activity of Cu/GE catalysts. The more amount of surface Cu species and highly dispersed CuO particles on the graphene surface formed by using copper nitrate as precursor could significantly improve the reducibility of catalysts and enhance NH3 adsorption, thereby improving the catalytic activity of Cu/graphene catalyst.

Functionalized Ni@SiO2 core/shell magnetic nanoparticles as a chemosensor and adsorbent for Cu2+ ion in drinking water and human blood.

PubMed

Park, Minsung; Seo, Sungmin; Lee, Soo Jin; Jung, Jong Hwa

2010-11-01

Fluorogenic based nitrobenzofuran-functionalized Ni@SiO(2) core/shell magnetic nanoparticles have been prepared by sol-gel grafting reaction. Their ability to detect and remove metal ions was evaluated by fluorophotometry. The nanoparticles exhibited a high affinity and selectivity for Cu(2+) over competing metal ions. Furthermore, the nanoparticles efficiently removed Cu(2+) in drinking water and human blood.

Spin rotational symmetry breaking by orbital current patterns in two-leg Cu-O Hubbard ladders

NASA Astrophysics Data System (ADS)

Chudzinski, Piotr; Gabay, Marc; Giamarchi, Thierry

2010-03-01

In the weak-coupling limit, we study, as a function of doping, two-leg ladders with a unit cell containing both Cu and O atoms. For purely repulsive interactions, using bosonization and a novel RG scheme, we find that in a broad region of the phase diagram, the ground state consists of a pattern of orbital currents (OCP) defined on the top of an incommensurate density wave. The internal symmetry of the OCP is specific for the ladder structure, different than the ones suggested up to now for 2D cuprates. We focus on this OCP and look for measurable signals of its existence: we compute magnetic fields induced within the ladder and we check what kind of changes in the phase diagram one may expect due to SU(2) spin-rotational symmetry breaking. We also investigate a single impurity problem (incl. OCP): we discuss if Kondo physics is at play, and make qualitative predictions about the nature of impurity backscattering. This enables us to show the influence of SU(2) symmetry breaking on conductivity. We estimate the value of gap opened due to the OCP, give analytic expressions for correlation functions and discuss magnetic properties of a new phase.

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.

Copper tolerance of the biomass crops Elephant grass (Pennisetum purpureum Schumach), Vetiver grass (Vetiveria zizanioides) and the upland reed (Phragmites australis) in soil culture.

PubMed

Liu, Xinghua; Shen, Yixing; Lou, Laiqing; Ding, Chenglong; Cai, Qingsheng

2009-01-01

Pot trials were conducted to study the influence of copper (Cu) on the growth and biomass of Elephant grass (EG, Pennisetum purpureum Schumach), Vetiver grass (VG, Vetiveria zizanioides) and the upland reed (UR, Phragmites australis). Cu toxicity in EG, VG and UR was positively correlated with the total and bioavailable Cu concentrations in the soil. Based on the EC50, dry weights, Cu contents, chlorophyll contents and photosynthesis rates, the Cu tolerance of the three species followed the trend EGNVGNUR. There were no significant differences in the unit calorific values among the different plants, though the total calorific values of EG were higher than those of VG and UR due to its higher biomass. The addition of KH2PO4 to the soil decreased the bioavailability of Cu and the Cu uptake by plants. EG could therefore be a good candidate for growth on Cu-contaminated soils, especially those improved by phosphate.

Effects of copper source and concentration on in vitro phytate phosphorus hydrolysis by phytase.

PubMed

Pang, Yanfang; Applegate, Todd J

2006-03-08

Five copper (Cu) sources were studied at pH 2.5, 5.5, and 6.5 to determine how Cu affects phytate phosphorus (PP) hydrolysis by phytase at concentrations up to 500 mg/kg diet (60 min, 40-41 degrees C). Subsequently, Cu solubility with and without sodium phytate was measured. Adding Cu inhibited PP hydrolysis at pH 5.5 and pH 6.5 (P < 0.05). This inhibition was greater with higher concentrations of Cu. Tri-basic copper chloride and copper lysinate inhibited PP hydrolysis much less than copper sulfate pentahydrate, copper chloride, and copper citrate (P < 0.05). A strong negative relationship was observed between PP hydrolysis and soluble Cu at pH 5.5 (r = -0.76, P < 0.0001) and 6.5 (r = -0.54, P < 0.0001). In conclusion, pH, Cu concentration, and source influenced PP hydrolysis by phytase in vitro and were related to the amount of soluble Cu and the formation of insoluble copper-phytin complexes.

Aluminum alloy anode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

Sun, Z. H.; Chen, Z. F.; Fu, Q. W.; Jiang, X. Y.

2017-03-01

Aluminum has larger theoretical capacity of 2235 mAh/g than that of graphite (372 mAh/g), but it has big disadvantages including shorter cycle life and higher irreversible capacity loss. Improving cycle performance can be obtained via alloying of aluminum. In this paper, two ternary aluminum alloy, Al7Cu2Fe and Al73Cu5Fe22 were prepared. The main phase of Al7Cu2Fe alloy was Al7Cu2Fe. The heat treatment increased the proportion of Al7Cu2Fe. The main phase of Al73Cu5Fe22 alloy was Al60Cu30Fe10. The heat treatment reduced the proportion of Al60Cu30Fe10. For two alloys, the heat treatment could increase discharge capacity compared with cast alloy. The discharge capacity was improved by 50%. The content of aluminum in alloys has little effect on improving cycle performance, and it has obvious influence on the phase structure of alloy with heat treatment.

Influence of carbon content on the copper-telluride phase formation and on the resistive switching behavior of carbon alloyed Cu-Te conductive bridge random access memory cells

NASA Astrophysics Data System (ADS)

Devulder, Wouter; Opsomer, Karl; Franquet, Alexis; Meersschaut, Johan; Belmonte, Attilio; Muller, Robert; De Schutter, Bob; Van Elshocht, Sven; Jurczak, Malgorzata; Goux, Ludovic; Detavernier, Christophe

2014-02-01

In this paper, we investigate the influence of the carbon content on the Cu-Te phase formation and on the resistive switching behavior in carbon alloyed Cu0.6Te0.4 based conductive bridge random access memory (CBRAM) cells. Carbon alloying of copper-tellurium inhibits the crystallization, while attractive switching behavior is preserved when using the material as Cu-supply layer in CBRAM cells. The phase formation is first investigated in a combinatorial way. With increasing carbon content, an enlargement of the temperature window in which the material stays amorphous was observed. Moreover, if crystalline phases are formed, subsequent phase transformations are inhibited. The electrical switching behavior of memory cells with different carbon contents is then investigated by implementing them in 580 μm diameter dot TiN/Cu0.6Te0.4-C/Al2O3/Si memory cells. Reliable switching behavior is observed for carbon contents up to 40 at. %, with a resistive window of more than 2 orders of magnitude, whereas for 50 at. % carbon, a higher current in the off state and only a small resistive window are present after repeated cycling. This degradation can be ascribed to the higher thermal and lower drift contribution to the reset operation due to a lower Cu affinity towards the supply layer, leading cycle-after-cycle to an increasing amount of Cu in the switching layer, which contributes to the current. The thermal diffusion of Cu into Al2O3 under annealing also gives an indication of the Cu affinity of the source layer. Time of flight secondary ion mass spectroscopy was used to investigate this migration depth in Al2O3 before and after annealing, showing a higher Cu, Te, and C migration for high carbon contents.

Efficient photocatalytic degradation of tetrabromodiphenyl ethers and simultaneous hydrogen production by TiO2-Cu2O composite films in N2 atmosphere: Influencing factors, kinetics and mechanism.

PubMed

Hu, Zhe; Wang, Xi; Dong, Haitai; Li, Shangyi; Li, Xukai; Li, Laisheng

2017-10-15

TiO 2 -Cu 2 O photocatalyst composite film with a heterostructure was synthesized on a copper substrate for 2,2',4,4'-tetrabromodiphenyl ether (BDE47) reduction. First, Cu 2 O film was synthesized by the electrochemical deposition method, and then TiO 2 was coated on the surface of the Cu 2 O film. The morphology, surface chemical composition and optical characteristics of TiO 2 -Cu 2 O film were characterized. The degradation efficiency of BDE47 and hydrogen production by TiO 2 -Cu 2 O films was higher than those by pure TiO 2 or Cu 2 O films. The highest BDE47 degradation efficiency of 90% and hydrogen production of 12.7mmolL liq -1 after 150min were achieved by 67%TiO 2 -Cu 2 O films. The influencing factors were investigated in terms of film component, solvent condition, and initial pH. A kinetics study demonstrated that BDE47 degradation followed a pseudo-first-order model. Photocatalytic apparent reaction rate constant of BDE47 by TiO 2 -Cu 2 O films was 0.0070min -1 , which was 3.3 times of that by directly photolysis process. During photocatalytic debrmination process, the photogenerated holes were reserved in the valance band of Cu 2 O to oxidize methanol. Meanwhile, the partial photogenerated electrons transferred to the conduction band of TiO 2 and directly eliminated the ortho-Br of BDE47 and yielded BDE28 and BDE15. The other partial photogenerated electrons reduced protons (H + ) to form atomic hydrogen (H°), which could substitute the para-Br of BDE47 and generated BDE17 and produce hydrogen. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of compositions on thermal stability and thermodynamic parameter in Ca-Mg-Cu bulk metallic glasses

NASA Astrophysics Data System (ADS)

Deshmukh, A. A.; Khond, A. A.; Palikundwar, U. A.

2018-05-01

In the present manuscript, influence of compositions on thermal stability (ΔTx) and thermodynamic parameter PHSS of Ca-Mg-Cu bulk metallic glasses (BMGs) is evaluated. The statistical approach of regression analysis is adopted to investigate the compositional variation with ΔTx and PHSS. It is found that calcium (Ca) and copper (Cu) content has goodlinear relationship with ΔTx and PHSS. It is observed that with increase in Ca content, ΔTx and PHSS decreases. On the other hand, increase in Cu content, both ΔTx and PHSS increases. Correlation fit of magnesium (Mg) content with both ΔTx and PHSS is very poor. A graph is also plotted to understand the relationship between ΔTx and PHSS. Result of the relationship between ΔTx and PHSS reveals that the alloy composition having more negative value of PHSS will have more stability. Therefore, compositions with more negative value of PHSS will lead to ease of BMGs formation in Ca-Mg-Cu alloy system and hence more stable it will be. It is expected that these results will be supportive in identifying the compositions having these elements for making BMGs.

Exploring low-temperature dehydrogenation at ionic Cu sites in beta zeolite to enable alkane recycle in dimethyl ether homologation

DOE PAGES

Farberow, Carrie A.; Cheah, Singfoong; Kim, Seonah; ...

2017-04-24

Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Bronsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. Furthermore, these results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C 5+) hydrocarbon yield.

Transcriptional and Functional Studies of Acidithiobacillus ferrooxidans Genes Related to Survival in the Presence of Copper▿

PubMed Central

Navarro, Claudio A.; Orellana, Luis H.; Mauriaca, Cecilia; Jerez, Carlos A.

2009-01-01

The acidophilic Acidithiobacillus ferrooxidans can resist exceptionally high copper (Cu) concentrations. This property is important for its use in biomining processes, where Cu and other metal levels range usually between 15 and 100 mM. To learn about the mechanisms that allow A. ferrooxidans cells to survive in this environment, a bioinformatic search of its genome showed the presence of at least 10 genes that are possibly related to Cu homeostasis. Among them are three genes coding for putative ATPases related to the transport of Cu (A. ferrooxidans copA1 [copA1Af], copA2Af, and copBAf), three genes related to a system of the resistance nodulation cell division family involved in the extraction of Cu from the cell (cusAAf, cusBAf, and cusCAf), and two genes coding for periplasmic chaperones for this metal (cusFAf and copCAf). The expression of most of these open reading frames was studied by real-time reverse transcriptase PCR using A. ferrooxidans cells adapted for growth in the presence of high concentrations of Cu. The putative A. ferrooxidans Cu resistance determinants were found to be upregulated when this bacterium was exposed to Cu in the range of 5 to 25 mM. These A. ferrooxidans genes conferred to Escherichia coli a greater Cu resistance than wild-type cells, supporting their functionality. The results reported here and previously published data strongly suggest that the high resistance of the extremophilic A. ferrooxidans to Cu may be due to part or all of the following key elements: (i) a wide repertoire of Cu resistance determinants, (ii) the duplication of some of these Cu resistance determinants, (iii) the existence of novel Cu chaperones, and (iv) a polyP-based Cu resistance system. PMID:19666734

Matrix effects on copper(II)phthalocyanine complexes. A combined continuous wave and pulse EPR and DFT study.

PubMed

Finazzo, Cinzia; Calle, Carlos; Stoll, Stefan; Van Doorslaer, Sabine; Schweiger, Arthur

2006-04-28

The effect of the electron withdrawing or donating character of groups located at the periphery of the phthalocyanine ligand, as well as the influence of polar and nonpolar solvents are of importance for the redox chemistry of metal phthalocyanines. Continuous wave and pulse electron paramagnetic resonance and pulse electron nuclear double resonance spectroscopy at X- and Q-band are applied to investigate the electronic structure of the complexes Cu(II)phthalocyanine (CuPc), copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPc(t)), and copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine (CuPc(F)) in various matrices. Isotope substitutions are used to determine the g values, the copper hyperfine couplings and the hyperfine interactions with the 14N, 1H and 19F nuclei of the macrocycle and the surrounding matrix molecules. Simulations and interpretations of the spectra are shown and discussed, and a qualitative analysis of the data using previous theoretical models is given. Density functional computations facilitate the interpretation of the EPR parameters. The experimental g, copper and nitrogen hyperfine and nuclear quadrupole values are found to be sensitive to changes of the solvent and the structure of the macrocycle. To elucidate the electronic, structural and bonding properties the changes in the g principal values are related to data from UV/Vis spectroscopy and to density functional theory (DFT) computations. The analysis of the EPR data indicates that the in-plane metal-ligand sigma bonding is more covalent for CuPc(t) in toluene than in sulfuric acid. Furthermore, the out-of-plane pi bonding is found to be less covalent in the case of a polar sulfuric acid environment than with nonpolar toluene or H2Pc environment, whereby the covalency of this bonding is increased upon addition of tert-butyl groups. No contribution from in-plane pi bonding is found.

The DFT Calculations of Structures and EPR Parameters for the Dinuclear Paddle-Wheel Copper(II) Complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) as Powder or Single Crystal

NASA Astrophysics Data System (ADS)

Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua

2017-10-01

Density functional theory (DFT) calculations of the structures and the Cu2+ g factors (gx, gy and gz ) and hyperfine coupling tensor A (Ax , Ay and Az ) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

Retrieval of Sentence Relations: Semantic vs. Syntactic Deep Structure.

ERIC Educational Resources Information Center

Perfetti, Charles A.

Two experiments on unaided and cued recall of sentences presented in context to college students are reported in this study. Key nouns in the sentences were arranged to have uniform surface functions, but to vary independently in deep syntactic category and semantic function. Cued recall for sentences in which the semantic function of actor and…

Effect of Isothermal Aging and Thermal Cycling on Interfacial IMC Growth and Fracture Behavior of SnAgCu/Cu Joints

NASA Astrophysics Data System (ADS)

Li, Xiaoyan; Li, Fenghui; Guo, Fu; Shi, Yaowu

2011-01-01

The growth behavior of interfacial intermetallic compounds (IMCs) of SnAgCu/Cu soldered joints was investigated during the reflow process, isothermal aging, and thermal cycling with a focus on the influence of these parameters on growth kinetics. The SnAgCu/Cu soldered joints were isothermally aged at 125°C, 150°C, and 175°C while the thermal cycling was performed within the temperature ranges from -25°C to 125°C and -40°C to 125°C. It was observed that a Cu6Sn5 layer formed, followed by rapid coarsening at the solder/Cu interface during reflowing. The grain size of the interfacial Cu6Sn5 was found to increase with aging time, and the morphology evolved from scallop-like to needle-like to rod-like and finally to particles. The rod-like Ag3Sn phase was formed on the solder side in front of the previously formed Cu6Sn5 layer. However, when subject to an increase of the aging time, the Cu3Sn phase was formed at the interface of the Cu6Sn5 layer and Cu substrate. The IMC growth rate increased with aging temperature for isothermally aged joints. During thermal cycling, the thickness of the IMC layer was found to increase with the number of thermal cycles, although the growth rate was slower than that for isothermal aging. The dwell time at the high-temperature end of the thermal cycles was found to significantly influence the growth rate of the IMCs. The growth of the IMCs, for both isothermal aging and thermal cycling, was found to be Arrhenius with aging temperature, and the corresponding diffusion factor and activation energy were obtained by data fitting. The tensile strength of the soldered joints decreased with increasing aging time. Consequently, the fracture site of the soldered joints migrated from the solder matrix to the interfacial Cu6Sn5 layer. Finally, the shear strength of the joints was found to decrease with both an increase in the number of thermal cycles and a decrease in the dwell temperature at the low end of the thermal cycle.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

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

Xue, Meng; Nakayama, Miki; Liu, Ping

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE PAGES

Xue, Meng; Nakayama, Miki; Liu, Ping; ...

2017-09-13

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Cu(II)-Doped Polydopamine-Coated Gold Nanorods for Tumor Theranostics.

PubMed

Liu, Shuwei; Wang, Lu; Lin, Min; Wang, Dandan; Song, Ziqi; Li, Shuyao; Ge, Rui; Zhang, Xue; Liu, Yi; Li, Zhimin; Sun, Hongchen; Yang, Bai; Zhang, Hao

2017-12-27

Gold nanorods (AuNRs) are potentially useful in tumor theranostics, but the poor stability, high toxicity, and rapid removal by the immune system seriously limit their theranostic applications. In our study, we demonstrate the fabrication of Cu(II)-doped polydopamine-coated AuNR (AuNR@CuPDA), which significantly improves the potentials in tumor theranostics. Besides the improvement of physiological stability and biocompatibility, the PDA shell increases the photothermal performance and prolongs the blood circulation time of AuNRs. The half-life of AuNRs during blood circulation increases from 0.7 to 4.5 h after PDA coating, and the injected dose per gram of tumor tissue is 4.6% ID g -1 for AuNR@CuPDA. In addition to computer tomography imaging, the loading of Cu(II) in PDA shell endows AuNR@CuPDA with magnetic resonance imaging function. Cu(II) doped in PDA shell also exhibits chemotherapeutic behavior, and the tumor inhibitor rate is 31.2%. Further combining 808 nm laser-driven photothermal therapy, tumors were completely ablated, and no recurrence was observed. Liver and renal functions tests and histological analysis of major organs confirm that AuNR@CuPDA is in good safety.

Boron doping effect on the interface interaction and mechanical properties of graphene reinforced copper matrix composite

NASA Astrophysics Data System (ADS)

Fang, Bingcheng; Li, Jiajun; Zhao, Naiqin; Shi, Chunsheng; Ma, Liying; He, Chunnian; He, Fang; Liu, Enzuo

2017-12-01

In order to explore an efficient way of modifying graphene to improve the Cu/graphene interfacial bonding and remain the excellent mechanical and physical properties of graphene, the interaction between Cu and the pristine, atomic oxygen functionalized and boron- or nitrogen-doped graphene with and without defects was systematically investigated by density functional theory calculation. The electronic structure analysis revealed that the chemically active oxygen can enhance the binding energy Eb of Cu with graphene by forming strong covalent bonds, supporting the experimental study suggesting an vital role of intermediate oxygen in the improvement of the mechanical properties of graphene/Cu composites. Due to the strong hybridization between Cu-3d electron states and the 2p states of both boron and carbon atoms, the boron-doping effect is comparable to or even better than the chemical bridging role of oxygen in the reduced graphene oxide reinforced Cu matrix composite. Furthermore, we evidenced an enhancement of mechanical properties including bulk modulus, shear modulus and Young modulus of graphene/Cu composite after boron doping, which closely relates to the increased interfacial binding energy between boron-doped graphene and Cu surfaces.

Wsbnd Cu functionally graded material: Low temperature fabrication and mechanical characterization

NASA Astrophysics Data System (ADS)

Yusefi, Ali; Parvin, Nader; Mohammadi, Hossein

2018-04-01

In this study, we fabricated and characterized a Wsbnd Cu functionally graded material (FGM) with 11 layers, including a pure copper layer. Samples were prepared by mixing a mechanically alloyed Nisbnd Mnsbnd Cu powder with W and Cu powders, stacking the powders, pressing the stacked layers, and finally sintering at 1000 °C. The utilization of a Nisbnd Mnsbnd Cu system may reduce the cost but without losing the good sintering behavior and physical and mechanical properties. The composition of the material was analyzed based on scanning electron microscopy images and by energy dispersive X-ray spectroscopy mapping, which indicated that in the presence of Ni and Mn, the Cu atoms could diffuse into the W particles. All of the layers had a very high relative density, thereby indicating their densification and excellent sintering behavior. We also found that the porosity values in the Cu phase remained unchanged at approximately 2.39% across the FGM. Mechanical measurements showed that the hardness (72%), modulus of elasticity (61%), and ultimate tensile strength (58%) increased with the W content across the Wsbnd Cu FGM, whereas the fracture toughness (KIC) varied in the opposite manner (minimum of 4.52 MPa/m0.5).

Scientific Understanding of Non-Chromated Corrosion Inhibitors Function

DTIC Science & Technology

2013-01-01

deposited Al - Cu thin films (left) and aged Al - Cu thin films (right). 348 Figure 7.8. Pit morphologies developed...under neat epoxy resins applied to “as- deposited ” (left) and aged Al - Cu thin films (right) at different exposure times. 349 Figure 7.9. SEM and EDS...results of “As- deposited ” Al - Cu thin film. 351 Figure 7.10. SEM and EDS results of aged Al - Cu thin films. 352 Figure 7.11. Pit

Early histological and functional effects of chronic copper exposure in rat liver.

PubMed

Cisternas, Felipe A; Tapia, Gladys; Arredondo, Miguel; Cartier-Ugarte, Denise; Romanque, Pamela; Sierralta, Walter D; Vial, María T; Videla, Luis A; Araya, Magdalena

2005-10-01

Cu is an essential trace element capable of producing toxic effects in animals and man when ingested acutely or chronically in excess. Although chronic Cu exposure is increasingly recognized as a public health issue, its early effects remain largely unknown. We approached the significance of a moderate chronic Cu load in young rats to correlate early hepatic histopathological changes with functional alterations of liver cells. For this purpose, supplementation with 1,200 ppm of Cu in rat food for 16 weeks was chosen. In these conditions, Cu load elicited a significant decrease in growth curves. There were mild light microscopy alterations in Cu-treated rats, although increasing intracellular Cu storage was correlated with longer Cu exposure both by histological and biochemical measurements. Ultrastructural alterations included lysosomal inclusions as well as mitochondrial and nuclear changes. Liver perfusion studies revealed higher rates of basal O(2) consumption and colloidal carbon-induced O(2) uptake in Cu-treated rats, with enhanced carbon-induced O(2)/carbon uptake ratios and NF-kappaB DNA binding activity. These changes were time-dependent and returned to control values after 12 or 16 weeks. It is concluded that subchronic Cu loading in young rats induces early hepatic morphological changes, with enhancement in Küpffer cell-dependent respiratory burst activity and NF-kappaB DNA binding, cellular responses that may prevent or alleviate the hepatotoxicity of the metal.

Synthesis and Biomedical Applications of Copper Sulfide Nanoparticles: From Sensors to Theranostics

PubMed Central

Goel, Shreya; Chen, Feng; Cai, Weibo

2013-01-01

Copper sulfide (CuS) nanoparticles have attracted increasing attention from biomedical researchers across the globe, because of their intriguing properties which have been mainly explored for energy- and catalysis-related applications to date. This focused review article aims to summarize the recent progress made in the synthesis and biomedical applications of various CuS nanoparticles. After a brief introduction to CuS nanoparticles in the first section, we will provide a concise outline of the various synthetic routes to obtain different morphologies of CuS nanoparticles, which can influence their properties and potential applications. CuS nanoparticles have found broad applications in vitro, especially in the detection of biomolecules, chemicals, and pathogens which will be illustrated in detail. The in vivo uses of CuS nanoparticles have also been investigated in preclinical studies, including molecular imaging with various techniques, cancer therapy based on the photothermal properties of CuS, as well as drug delivery and theranostic applications. Research on CuS nanoparticles will continue to thrive over the next decade, and tremendous opportunities lie ahead for potential biomedical/clinical applications of CuS nanoparticles. PMID:24106015

First principles calculations on the influence of solute elements and chlorine adsorption on the anodic corrosion behavior of Mg (0001) surface

NASA Astrophysics Data System (ADS)

Luo, Zhe; Zhu, Hong; Ying, Tao; Li, Dejiang; Zeng, Xiaoqin

2018-06-01

The influences of solute atoms (Li, Al, Mn, Zn, Fe, Ni, Cu, Y, Zr) and Cl adsorption on the anodic corrosion performance on Mg (0001) surface have been investigated based on first-principles calculations, which might be useful for the design of corrosion-resistant Mg alloys. Work function and local electrode potential shift are chosen as descriptors since they quantify the barrier for charge transfer and anodic stability. We found that at 25% surface doping rate, Y decreased the work function of Mg, while the impact of remaining doping elements on the work function of Mg was trivial due to the small surface dipole moment change. The adsorption of Cl destabilized the Mg atoms at surface by weakening the bonding between surface Mg atoms. We find that a stronger hybridization of d orbits of alloying elements (e.g. Zr) with the orbits of Mg can greatly increase the local electrode potential,which even overbalances the negative effect introduced by Cl adsorbates and hence improves the corrosion resistance of Mg alloys.

Synthesis and characterization of new nanocomposites films using alanine-Cu-functionalized graphene oxide as nanofiller and PVA as polymeric matrix for improving of their properties

NASA Astrophysics Data System (ADS)

Abdolmaleki, Amir; Mallakpour, Shadpour; Karshenas, Azam

2017-09-01

In the synthesis of polymer-graphene nanocomposites, for improving properties of nanocomposites, two factors dispersion and strong interfacial interactions between graphene and the polymer, are essential. In the present work, poly(vinyl alcohol) PVA/GO-Cu-alanine nanocomposite films were manufactured using concentrations 0, 1, 3 and 5 wt% of GO-Cu-alanine in water solution. For this purpose, L-alanine amino acid was located on the surface and edges of GO through copper(II) ion as a coordinating function. Then, flexible PVA/GO-Cu-alanine nanocomposite films were fabricated using GO-Cu-alanine as filler and PVA as matrix. Due to the existence of affective interaction between GO-Cu-alanine and PVA matrix, the acquired PVA/GO-Cu-alanine nanocomposites demonstrated great thermal and mechanical properties. Properties of manufactured materials were characterized by Fourier transform infrared, X-ray photoelectron spectroscopies (XPS), X-ray diffraction (XRD), Thermal gravimetric analysis, elemental analysis, field emission scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy (EDX).

Copper cluster size effect in methanol synthesis from CO 2

DOE PAGES

Yang, Bing; Liu, Cong; Halder, Avik; ...

2017-05-08

Here, size-selected Cu n catalysts ( n = 3, 4, 20) were synthesized on Al 2O 3 thin films using mass-selected cluster deposition. A systematic study of size and support effects was carried out for CO 2 hydrogenation at atmospheric pressure using a combination of in situ grazing incidence X-ray absorption spectroscopy, catalytic activity measurement, and first-principles calculations. The catalytic activity for methanol synthesis is found to strongly vary as a function of the cluster size; the Cu 4/Al 2O 3 catalyst shows the highest turnover rate for CH 3OH production. With only one atom less than Cu 4, Cumore » 3 showed less than 50% activity. Density functional theory calculations predict that the activities of the gas-phase Cu clusters increase as the cluster size decreases; however, the stronger charge transfer interaction with Al 2O 3 support for Cu 3 than for Cu 4 leads to remarkably reduced binding strength between the adsorbed intermediates and supported Cu 3, which subsequently results in a less favorable energetic pathway to transform carbon dioxide to methanol.« less

Comparing Ullmann Coupling on Noble Metal Surfaces: On-Surface Polymerization of 1,3,6,8-Tetrabromopyrene on Cu(111) and Au(111).

PubMed

Pham, Tuan Anh; Song, Fei; Nguyen, Manh-Thuong; Li, Zheshen; Studener, Florian; Stöhr, Meike

2016-04-18

The on-surface polymerization of 1,3,6,8-tetrabromopyrene (Br4 Py) on Cu(111) and Au(111) surfaces under ultrahigh vacuum conditions was investigated by a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Deposition of Br4 Py on Cu(111) held at 300 K resulted in a spontaneous debromination reaction, generating the formation of a branched coordination polymer network stabilized by C-Cu-C bonds. After annealing at 473 K, the C-Cu-C bonds were converted to covalent C-C bonds, leading to the formation of a covalently linked molecular network of short oligomers. In contrast, highly ordered self-assembled two-dimensional (2D) patterns stabilized by both Br-Br halogen and Br-H hydrogen bonds were observed upon deposition of Br4 Py on Au(111) held at 300 K. Subsequent annealing of the sample at 473 K led to a dissociation of the C-Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann reaction, but also influences the formation of different types of intermolecular bonds and thus, determines the final polymer network morphology. DFT calculations further support our experimental findings obtained by STM and XPS and add complementary information on the reaction pathway of Br4 Py on the different substrates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of silica-supported porous sorbent for heavy metal ions removal in wastewater treatment by organic-inorganic hybridization combined with sucrose and polyethylene glycol imprinting.

PubMed

Li, Feng; Du, Ping; Chen, Wei; Zhang, Shusheng

2007-03-07

A new porous sorbent for wastewater treatment of metal ions was synthesized by covalent grafting of molecularly imprinted organic-inorganic hybrid on silica gel. With sucrose and polyethylene glycol 4000 (PEG 4000) being synergic imprinting molecules, covalent surface coating on silica gel was achieved by using polysaccharide-incorporated sol-gel process starting from the functional biopolymer, chitosan and an inorganic epoxy-precursor, gamma-glycidoxypropyltrimethoxysiloxane (GPTMS) at room temperature. The prepared porous sorbent was characterized by using simultaneous thermogravimetry and differential scanning calorimeter (TG/DSC), scanning electron microscopy (SEM), nitrogen adsorption porosimetry measurement and X-ray diffraction (XRD). Copper ion, Cu(2+), was chosen as the model metal ion to evaluate the effectiveness of the new biosorbent in wastewater treatment. The influence of epoxy-siloxane dose, buffer pH and co-existed ions on Cu(2+) adsorption was assessed through batch experiments. The imprinted composite sorbent offered a fast kinetics for the adsorption of Cu(2+). The uptake capacity of the sorbent imprinted by two pore-building components was higher than those imprinted with only a single component. The dynamic adsorption in column underwent a good elimination of Cu(2+) in treating electric plating wastewater. The prepared composite sorbent exhibited high reusability. Easy preparation of the described porous composite sorbent, absence of organic solvents, cost-effectiveness and high stability make this approach attractive in biosorption.

Optimizing protease production from an isolate of the nematophagous fungus Duddingtonia flagrans using response surface methodology and its larvicidal activity on horse cyathostomins.

PubMed

Braga, F R; Araújo, J V; Soares, F E F; Araujo, J M; Genier, H L A; Silva, A R; Carvalho, R O; Queiroz, J H; Ferreira, S R

2011-06-01

Protease production from Duddingtonia flagrans (isolate AC001) was optimized and the larvicidal activity of the enzymatic extract was evaluated on infective horse cyathostomin larvae (L3). Duddingtonia flagrans was grown in liquid medium with eight different variables: glucose, casein, bibasic potassium phosphate (K2HPO4), magnesium sulphate (MgSO4), zinc sulphate (ZnSO4), ferrous sulphate (FeSO4), copper sulphate (CuSO4) and temperature. The Plackett-Burman analysis showed a significant influence of MgSO4, CuSO4 and casein (P < 0.05) on protease production by D. flagrans in liquid medium. Central composite design indicated that the highest proteolytic activity was 39.56 U/ml as a function of the concentrations of casein (18.409 g/l), MgSO4 (0.10 g/l) and CuSO4 (0.50 mg/l). A significant difference (P < 0.01) was found for the larval number between the treated and control groups at the end of the experiment. A reduction of 95.46% in the number of free-living larvae was found in the treated group compared with the control. The results of this study suggest that protease production by D. flagrans (AC001) in liquid medium was optimized by MgSO4, CuSO4 and casein, showing that the optimized enzymatic extract exerted larvicidal activity on cyathostomins and therefore may contribute to large-scale industrial production.

Unique Helicase Determinants in the Essential Conjugative TraI Factor from Salmonella enterica Serovar Typhimurium Plasmid pCU1

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

McLaughlin, K. J.; Nash, R. P.; Redinbo, M. R.

The widespread development of multidrug-resistant bacteria is a major health emergency. Conjugative DNA plasmids, which harbor a wide range of antibiotic resistance genes, also encode the protein factors necessary to orchestrate the propagation of plasmid DNA between bacterial cells through conjugative transfer. Successful conjugative DNA transfer depends on key catalytic components to nick one strand of the duplex DNA plasmid and separate the DNA strands while cell-to-cell transfer occurs. The TraI protein from the conjugative Salmonella plasmid pCU1 fulfills these key catalytic roles, as it contains both single-stranded DNA-nicking relaxase and ATP-dependent helicase domains within a single, 1,078-residue polypeptide. Inmore » this work, we unraveled the helicase determinants of Salmonella pCU1 TraI through DNA binding, ATPase, and DNA strand separation assays. TraI binds DNA substrates with high affinity in a manner influenced by nucleic acid length and the presence of a DNA hairpin structure adjacent to the nick site. TraI selectively hydrolyzes ATP, and mutations in conserved helicase motifs eliminate ATPase activity. Surprisingly, the absence of a relatively short (144-residue) domain at the extreme C terminus of the protein severely diminishes ATP-dependent strand separation. Collectively, these data define the helicase motifs of the conjugative factor TraI from Salmonella pCU1 and reveal a previously uncharacterized C-terminal functional domain that uncouples ATP hydrolysis from strand separation activity.« less

In Situ Study of Reduction Process of CuO Paste and Its Effect on Bondability of Cu-to-Cu Joints

NASA Astrophysics Data System (ADS)

Yao, Takafumi; Matsuda, Tomoki; Sano, Tomokazu; Morikawa, Chiaki; Ohbuchi, Atsushi; Yashiro, Hisashi; Hirose, Akio

2018-04-01

A bonding method utilizing redox reactions of metallic oxide microparticles achieves metal-to-metal bonding in air, which can be alternative to lead-rich high-melting point solder. However, it is known that the degree of the reduction of metallic oxide microparticles have an influence on the joint strength using this bonding method. In this paper, the reduction behavior of CuO paste and its effect on Cu-to-Cu joints were investigated through simultaneous microstructure-related x-ray diffraction and differential scanning calorimetry measurements. The CuO microparticles in the paste were gradually reduced to submicron Cu2O particles at 210-250°C. Subsequently, Cu nanoparticles were generated instantaneously at 300-315°C. There was a marked difference in the strengths of the joints formed at 300°C and 350°C. Thus, the Cu nanoparticles play a critical role in sintering-based bonding using CuO paste. Furthermore, once the Cu nanoparticles have formed, the joint strength increases with higher bonding temperature (from 350°C to 500°C) and pressure (5-15 MPa), which can exceed the strength of Pb-5Sn solder at higher temperature and pressure.

Statistical Analysis of Main and Interaction Effects on Cu(II) and Cr(VI) Decontamination by Nitrogen-Doped Magnetic Graphene Oxide

NASA Astrophysics Data System (ADS)

Hu, Xinjiang; Wang, Hui; Liu, Yunguo

2016-10-01

A nitrogen-doped magnetic graphene oxide (NMGO) was synthesized and applied as an adsorbent to remove Cu(II) and Cr(VI) ions from aqueous solutions. The individual and combined effects of various factors (A: pH, B: temperature, C: initial concentration of metal ions, D: CaCl2, and E: humic acid [HA]) on the adsorption were analyzed by a 25-1 fractional factorial design (FFD). The results from this study indicated that the NMGO had higher adsorption capacities for Cu(II) ions than for Cr(VI) ions under most conditions, and the five selected variables affected the two adsorption processes to different extents. A, AC, and C were the very important factors and interactions for Cu(II) adsorption. For Cr(VI) adsorption, A, B, C, AB, and BC were found to be very important influencing variables. The solution pH (A) was the most important influencing factor for removal of both the ions. The main effects of A-E on the removal of Cu(II) were positive. For Cr(VI) adsorption, the main effects of A and D were negative, while B, C, and E were observed to have positive effects. The maximum adsorption capacities for Cu(II) and Cr(VI) ions over NMGO were 146.365 and 72.978 mg/g, respectively, under optimal process conditions.

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

NASA Astrophysics Data System (ADS)

Amal, Muhamad I.; Kim, Kyoo Ho

2013-12-01

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

A mechanism of Cu work function reduction in CsBr/Cu photocathodes

DOE PAGES

Halliday, M. T. E.; Hess, W. P.; Shluger, A. L.

2016-02-15

Thin films of CsBr deposited on Cu(100) have been proposed as next-generation photocathode materials for applications in particle accelerators and free-electron lasers. However, the mechanisms underlying an improved photocathode performance remain poorly understood. We present density Functional Theory (DFT) calculations of the work function reduction following the application of CsBr thin film coatings to Cu photocathodes. The effects of structure and van der Waals forces are examined. Calculations suggest that CsBr films can reduce the work function by around 1.5 eV, which would explain the exponential increase in quantum efficiency (QE) of coated vs. uncoated photocathodes. In conclusion, a modelmore » explaining experimentally observed laser activation of photocathode is provided whereby the photo-induced creation of di-vacancies at the surface, and their subsequent diffusion throughout the lattice and segregation at the interface leads to a further increase in QE after a period of laser irradiation.« less

Metal-ligand delocalization and spin density in the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} molecules: Some insights from wave function theory

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

Giner, Emmanuel, E-mail: gnrmnl@unife.it; Angeli, Celestino, E-mail: anc@unife.it

2015-09-28

The aim of this paper is to unravel the physical phenomena involved in the calculation of the spin density of the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} systems using wave function methods. Various types of wave functions are used here, both variational and perturbative, to analyse the effects impacting the spin density. It is found that the spin density on the chlorine ligands strongly depends on the mixing between two types of valence bond structures. It is demonstrated that the main difficulties found in most of the previous studies based on wave function methods come from the fact that eachmore » valence bond structure requires a different set of molecular orbitals and that using a unique set of molecular orbitals in a variational procedure leads to the removal of one of them from the wave function. Starting from these results, a method to compute the spin density at a reasonable computational cost is proposed.« less

Systematic study of azimuthal anisotropy in Cu + Cu and Au + Au collisions at √s NN = 62.4 and 200 GeV

DOE PAGES

Adare, A.

2015-09-23

We have studied the dependence of azimuthal anisotropy v 2 for inclusive and identified charged hadrons in Au+Au and Cu+Cu collisions on collision energy, species, and centrality. The values of v 2 as a function of transverse momentum pT and centrality in Au+Au collisions at √s NN=200 and 62.4 GeV are the same within uncertainties. However, in Cu+Cu collisions we observe a decrease in v 2 values as the collision energy is reduced from 200 to 62.4 GeV. The decrease is larger in the more peripheral collisions. By examining both Au+Au and Cu+Cu collisions we find that v 2 dependsmore » both on eccentricity and the number of participants, N part. We observe that v 2 divided by eccentricity (ε) monotonically increases with N part and scales as N 1/3 part. Thus, the Cu+Cu data at 62.4 GeV falls below the other scaled v 2 data. For identified hadrons, v 2 divided by the number of constituent quarks nq is independent of hadron species as a function of transverse kinetic energy KE T=m T–m between 0.1T/n q<1 GeV. Combining all of the above scaling and normalizations, we observe a near-universal scaling, with the exception of the Cu+Cu data at 62.4 GeV, of v 2/(n q∙ε∙N 1/3 part) vs KE T/n q for all measured particles.« less

Interface characteristics at an organic/metal junction: pentacene on Cu stepped surfaces.

PubMed

Matos, Jeronimo; Kara, Abdelkader

2016-11-09

The adsorption of pentacene on Cu (2 2 1), Cu (5 1 1) and Cu (9 1 1) is investigated using density functional theory (DFT) with the self-consistent inclusion of van der Waals (vdW) interactions. Cu (2 1 1) is a vicinal of Cu (1 1 1) while Cu (5 1 1) and (9 1 1) are vicinals of Cu (1 0 0). For all the three surfaces, we found pentacene to prefer to adsorb parallel to the surface and near the steps. The addition of vdW interactions resulted in an enhancement in adsorption energies, with reference to the PBE functional, of around 2 eV. With vdWs inclusion, the adsorption energies were found to be 2.98 eV, 3.20 eV and 3.49 eV for Cu (2 2 1), Cu (5 1 1) and Cu (9 1 1) respectively. These values reflect that pentacene adsorbs stronger on (1 0 0) terraces with a preference for larger terraces. The molecule tilts upon adsorption with a small tilt angle on the (1 0 0) vicinals (about a few degrees) as compared to a large one on Cu (2 2 1) where the tilt angle is found to be about 20°. We find that the adsorption results in a net charge transfer to the molecule of ~1 electron, for all surfaces.

Cadets' swimming and running performance with and without a combat uniform.

PubMed

Kounalakis, Stylianos N; Kostoulas, Ioannis; Havenetidis, Konstantinos; Giossos, Ioannis; Paxinos, Thrasivoulos

2014-01-01

The aim was to examine whether a combat uniform (CU) influences the cadet's exercise performance in and out of the water. Fourteen male Army Officer cadets performed on 6 separate days: (1) a maximal 400-m freestyle swimming trial; (2) a 4 x 50-m all-out freestyle swimming trial with 10 s rest in between; (3) a 50-m swim obstacle course with a CU (CUs); (4) a 50-m swim obstacle course without a CU (NUs); (5) a 1000-m track run with a CU (CU(R)); and (6) a 1000-m track run without a CU (NUR). In each trial, performance time, oxygen uptake (Vo2), lactate concentration ([La]), and capillary oxygen saturation (SpO2) were recorded. The mean performance time was 44.3 +/- 3.1 s and 33.4 +/- 1.8 s in CUs and NUs trials, respectively. Peak VO2 was similar in CUs, NUs, and 400 m (CUs: 59.1 +/- 1.1 ml x kg(-1) x min(-1), NUs: 57.3 +/- 2.1 ml kg(-1) x min(-1), 400 m: 58.2 +/- 1.6 ml x kg(-1) min(-1)). [La] was higher in CUs than in NUs (CUs: 10.0 +/- 2.0 mmol x L(-1), NUs: 8.5 +/- 1.8 mmol x L(-1)), but it was lower in CUs and NUs than during the 400 m and 4 x 50 m. SpO2 was lower (approximately 4.5%) in CUs than NUs. No differences were observed between running trials. The results suggest that the use of CU during swimming tasks induces high demands for energy and, thus, leads to a significant impairment of the swimming performance of the cadets. However, the influence of the CU seems to be less crucial during dry land running performance.

[Oxidation behavior and kinetics of representative VOCs emitted from petrochemical industry over CuCeOx composite oxides].

PubMed

Chen, Chang-Wei; Yu, Yan-Ke; Chen, Jin-Sheng; He, Chi

2013-12-01

CuCeOx composite catalysts were synthesized via coprecipitation (COP-CuCeO,) and incipient impregnation (IMP-CuCeOx) methods, respectively. The physicochemical properties of the samples were characterized by XRD, low-temperature N2 sorption, H2-TPR and O2-TPD. The influences of reactant composition and concentration, reaction space velocity, O2 content, H2O concentration, and catalyst type on the oxidation behaviors of benzene, toluene, and n-hexane emitted from petrochemical industry were systematically investigated. In addition, the related kinetic parameters were model fitted. Compared with IMP-CuCeOx, COP-CuCeOx had well-dispersed active phase, better low-temperature reducibility, and more active surface oxygen species. The increase of reactant concentration was unfavorable for toluene oxidation, while the opposite phenomenon could be observed in n-hexane oxidation. The inlet concentration of benzene was irrelevant to its conversion under high oxidation rate. The introduction of benzene obviously inhibited the oxidation of toluene and n-hexane, while the presence of toluene had a positive effect on beuzene conversion. The presence of n-hexane could promote the oxidation of toluene, while toluene had a negative influence on e-hexane oxidation. Both low space velocity and high oxygen concentration were beneficial for the oxidation process, and the variation of oxygen content had negligible effect on n-hexane and henzene oxidation. The presence of H2O noticeably inhibited the oxidation of toluene, while significantly accelerated the oxidation procedure of henzene and n-hexane. COP-CuCeOx had superior catalytic performance for toluene and benzene oxidation, while IMP-CuCeOx showed higher n-hexane oxidation activity under dry condition. The oxidation behaviors under different conditions could be well fitted and predicted by the pseudo first-order kinetic model.

Modeling the interaction and toxicity of Cu-Cd mixture to wheat roots affected by humic acids, in terms of cell membrane surface characteristics.

PubMed

Wang, Yi-Min; Zhou, Dong-Mei; Yuan, Xu-Yin; Zhang, Xiao-Hui; Li, Yi

2018-05-01

Responses of wheat (Triticum aestivum L.) seedling roots to the mixtures of copper (Cu), cadmium (Cd) and humic acids (HA) were investigated using the solution culture experiments, focusing on the interaction patterns between multiple metals and their influences on root proton release. A concentration-addition multiplication (CA) model was introduced into the modeling analysis. In comparison with metal ion activities in bulk-phase solutions, the incorporation of ion activities at the root cell membrane surfaces (CMs) (denoted as {Cu 2+ } 0 and {Cd 2+ } 0 ) into the CA model could significantly improve their correlation with RRE (relative root elongation) from 0.819 to 0.927. Modeling analysis indicated that the co-existence of {Cu 2+ } 0 significantly enhanced the rhizotoxicity of {Cd 2+ } 0 , while no significant effect of {Cd 2+ } 0 on the {Cu 2+ } 0 rhizotoxicity. 10 mg/L HA stimulated the root elongation even under metal stress. Although high concentration of metal ions inhibited the root proton release rate (ΔH + ), both the low concentration of metal ions and HA treatments increased the values of ΔH + . In HA-Cu-Cd mixtures, actions of metal ions on ΔH + values were varied intricately among treatments but well modeled by the CA model. We concluded from the CA models that the electrostatic effect is vitally important for explaining the effect of {Cu 2+ } 0 on the rhizotoxicity of {Cd 2+ } 0 , while it plays no unique role in understanding the influence of {Cd 2+ } 0 on the rhizotoxicity of {Cu 2+ } 0. Thus our study provide a novel way for modeling multiple metals behaviors in the environment and understanding the mechanisms of ion interactions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Novel configuration of processing bulk textured YB 2Cu 3O 7-x superconductor by seeded infiltration growth method

NASA Astrophysics Data System (ADS)

Cao, Haitao; Moutalbi, Nahed; Harnois, Christelle; Hu, Rui; Li, Jinshan; Zhou, Lian; Noudem, Jacques G.

2010-01-01

Mono-domain YBa 2Cu 3O 7-x (Y123) bulk superconductors have been processed using seeded infiltration growth technique (SIG). The combination of melt infiltrated liquid source (Ba 3Cu 5O 8) into the Y 2BaCuO 5 (Y211) pre-form and the nucleation of Y123 domain from SmBa 2Cu 3O 7 crystal seed has been investigated. The different configurations of SIG process were compared in this study. In addition, the effect of the starting Y211 particles size has been studied. The results reveal that, the Y211 particle size and different configurations strongly influence the properties of the final bulk superconductor sample.

Influence of metal concentrations, percent salinity, and length of exposure on the metabolic rate of fathead minnows (Pimephales promelas).

PubMed

Pistole, David H; Peles, John D; Taylor, Kelly

2008-07-01

Understanding the effects of chemical toxicants on energetic processes is an important aspect of ecotoxicology. However, the influence of toxicant concentration and time of exposure on metabolism in aquatic organisms is still poorly understood. The purpose of this investigation was to determine the influence of increasing levels of three stressors (Cu, Cd, percent salinity) and exposure time (24 h and 96 h) on the metabolic rate of fathead minnows (Pimephales promelas). In all 24-h exposures, there existed a threshold concentration, above which metabolic rate decreased significantly compared to the control and lower concentrations. In contrast, the metabolic rate of fish exposed for 96 h increased significantly in all concentrations compared to fish from the control. We suggest fathead minnows exhibit a consistent pattern of metabolic response to stressors, regardless of the physiological mechanisms involved, and that this response differs as a function of time of exposure.

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

NASA Astrophysics Data System (ADS)

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

2009-06-01

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

Density functional theory meta-GGA + U study of water incorporation in the metal-organic framework material Cu-BTC.

PubMed

Cockayne, Eric; Nelson, Eric B

2015-07-14

Water absorption in the metal-organic framework (MOF) material Cu-BTC, up to a concentration of 3.5 H2O per Cu ion, is studied via density functional theory at the meta-GGA + U level. The stable arrangements of water molecules show chains of hydrogen-bonded water molecules and a tendency to form closed cages at high concentration. Water clusters are stabilized primarily by a combination of water-water hydrogen bonding and Cu-water oxygen interactions. Stability is further enhanced by van der Waals interactions, electric field enhancement of water-water bonding, and hydrogen bonding of water to framework oxygens. We hypothesize that the tendency to form such stable clusters explains the particularly strong affinity of water to Cu-BTC and related MOFs with exposed metal sites.

Density functional theory study of 3R- and 2H-CuAlO2 under pressure

NASA Astrophysics Data System (ADS)

Liu, Qi-Jun; Liu, Zheng-Tang; Feng, Li-Ping; Tian, Hao; Liu, Wen-Ting; Yan, Feng

2010-10-01

We present a first-principles density-functional theory based study of the impact of pressure on the structural and elastic properties of bulk 3R- and 2H-CuAlO2. The ground state properties of 3R- and 2H-CuAlO2 are obtained, which are in good agreement with previous experimental and theoretical data. The analysis of enthalpy variation with pressure indicates the phase transition pressure between 3R and 2H is 15.4 GPa. The independent elastic constants of 3R- and 2H-CuAlO2 are calculated. As the applied pressure increases, the calculations show the presences of mechanical instability at 26.2 and 27.8 GPa for 3R- and 2H-CuAlO2, which are possibly related with the phase transitions.

Parameterizing the binding properties of dissolved organic matter with default values skews the prediction of copper solution speciation and ecotoxicity in soil.

PubMed

Djae, Tanalou; Bravin, Matthieu N; Garnier, Cédric; Doelsch, Emmanuel

2017-04-01

Parameterizing speciation models by setting the percentage of dissolved organic matter (DOM) that is reactive (% r-DOM) toward metal cations at a single 65% default value is very common in predictive ecotoxicology. The authors tested this practice by comparing the free copper activity (pCu 2+  = -log 10 [Cu 2+ ]) measured in 55 soil sample solutions with pCu 2+ predicted with the Windermere humic aqueous model (WHAM) parameterized by default. Predictions of Cu toxicity to soil organisms based on measured or predicted pCu 2+ were also compared. Default WHAM parameterization substantially skewed the prediction of measured pCu 2+ by up to 2.7 pCu 2+ units (root mean square residual = 0.75-1.3) and subsequently the prediction of Cu toxicity for microbial functions, invertebrates, and plants by up to 36%, 45%, and 59% (root mean square residuals ≤9 %, 11%, and 17%), respectively. Reparametrizing WHAM by optimizing the 2 DOM binding properties (i.e., % r-DOM and the Cu complexation constant) within a physically realistic value range much improved the prediction of measured pCu 2+ (root mean square residual = 0.14-0.25). Accordingly, this WHAM parameterization successfully predicted Cu toxicity for microbial functions, invertebrates, and plants (root mean square residual ≤3.4%, 4.4%, and 5.8%, respectively). Thus, it is essential to account for the real heterogeneity in DOM binding properties for relatively accurate prediction of Cu speciation in soil solution and Cu toxic effects on soil organisms. Environ Toxicol Chem 2017;36:898-905. © 2016 SETAC. © 2016 SETAC.

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

PubMed

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

2016-06-02

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

Effect of the Cu/Ba ratio for the YBCO deposition onto IBAD template by the MOCVD method

NASA Astrophysics Data System (ADS)

Choi, J. K.; Kim, H. J.; Jun, B. H.; Kim, C. J.

2005-10-01

YBa2Cu3O7-x (YBCO) thin films were fabricated by the metal organic chemical vapor deposition (MOCVD) using a single liquid source. The copper/barium (Cu/Ba) ratio was varied from 1.26 to 1.38 to optimize the deposition condition. The IBAD template (CeO2/YSZ/stainless steel) was used as a substrate. The growth features of the YBCO films were not significantly influenced by the Cu/Ba ratio, while the superconducting transition temperature (Tc) and critical current (Ic) depended on the Cu/Ba ratio. When Cu/Ba ratio was between 1.26 and 1.29, Tc was as low as 80 K, while as Cu/Ba ratio increased to 1.38, it increased to above 85 K. The highest Tc (89.0 K) and Ic (46.3 A/cm-width) were achieved at the Cu/Ba ratio of 1.38 (Y:Ba:Cu = 1:2.1:2.9). It indicates that the optimum Cu/Ba ratio which differs from stoichiometric balance exists for the formation of the superconducting phase with a high Tc and Ic in MOCVD method.

[Kinetics of Cu crossing human erythrocyte membrane].

PubMed

Dun, Zhu Ci Ren

2014-12-01

This study was aimed to investigate various factors influencing the proceduction of Cu(II) crossing human erythrocyte membrane, including concentration of Cu²⁺, pH value of the medium, temperature and time of incubation, and to derive kinetic equation of Cu(II) crossing human erythrocyte membrane. Suspension red blood cells were incubated by Cu²⁺, then content of Cu²⁺ crossed human erythrocyte membrane was determined by atomic absorption spectrometry under various conditions after digestion. The results showed that content of Cu²⁺ crossed human erythrocyte membrane increased with the increase of extracellular Cu²⁺ and enhancement of incubation temperature, and the content of Cu²⁺ crossed human erythrocyte membrane showed a increasing tendency when pH reached to 6.2-7.4, and to maximum at pH 7.4, then gradually decreased at range of pH 7.4-9.2. It is concluded that the Cu²⁺ crossing human erythrocyte has been confirmed to be the first order kinetics characteristics within 120 min, and the linear equation is 10³ × Y = 0.0497t +6.5992.

Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions

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

Oakdale, James S.; Kwisnek, Luke; Fokin, Valery V.

2016-06-10

Functional polystyrenes and polyacrylamides, containing combinations of fluorosulfate, aromatic silyl ether, and azide side chains, were used as scaffolds to demonstrate the postpolymerization modification capabilities of sulfur(VI) fluoride exchange (SuFEx) and CuAAC chemistries. Fluorescent dyes bearing appropriate functional groups were sequentially attached to the backbone of the copolymers, quantitatively and selectively addressing their reactive partners. Furthermore, this combined SuFEx and CuAAC approach proved to be robust and versatile, allowing for a rare accomplishment: triple orthogonal functionalization of a copolymer under essentially ambient conditions without protecting groups.

Growth response, blood characteristics and copper accumulation in organs of broilers fed on diets supplemented with organic and inorganic dietary copper sources.

PubMed

Jegede, A V; Oduguwa, O O; Bamgbose, A M; Fanimo, A O; Nollet, L

2011-02-01

1. A 56-d experiment was conducted to study the comparative influence of organic and inorganic dietary copper (Cu) sources on growth, blood characteristics and copper accumulation in organs of broilers. 2. A total of 480 Arbor-Acre unsexed broilers were fed on diets containing copper sulphate (CuSO(4)) or copper proteinate (Cu Pro) at concentrations of 50, 100 or 150 mg/kg of Cu supplementation. The birds were given a broiler starter diet from 1-28 d and a broiler finisher diet from 29-56 d which contained 30·8 mg/kg and 41·1 mg/kg basal copper concentration respectively. Growth performance, blood characteristics and Cu accumulation in organs of the broilers were measured. 3. At 28 d, Cu Pro-fed birds had improved feed conversion ratio compared with CuSO(4). At 56 d, birds fed on Cu Pro diets had significantly greater body weight than CuSO(4)-fed birds. Birds fed on CuSO(4) supplemented diets had significantly better feed conversion efficiency. Feed consumptions for the two Cu sources were not significantly different. At no stage did the concentration of added Cu affect the productive traits measured. 4. Cu Pro supplementation increased haemoglobin concentration but reduced plasma triglyceride and plasma cholesterol. Plasma cholesterol decreased as Cu concentration increased. 5. There was a greater accumulation of Cu in the blood, heart, lung, liver and bone of broilers fed on Cu Pro than in those receiving CuSO(4). The liver Cu concentration increased as dietary Cu concentration increased. 6. Cu Pro was more effective in promoting growth and reducing blood cholesterol, and was more bio-available in the organs of broilers.

What can flies tell us about copper homeostasis?

PubMed

Southon, Adam; Burke, Richard; Camakaris, James

2013-10-01

Copper (Cu) is an essential redox active metal that is potentially toxic in excess. Multicellular organisms acquire Cu from the diet and must regulate uptake, storage, distribution and export of Cu at both the cellular and organismal levels. Systemic Cu deficiency can be fatal, as seen in Menkes disease patients. Conversely Cu toxicity occurs in patients with Wilson disease. Cu dyshomeostasis has also been implicated in neurodegenerative disorders such as Alzheimer's disease. Over the last decade, the fly Drosophila melanogaster has become an important model organism for the elucidation of eukaryotic Cu regulatory mechanisms. Gene discovery approaches with Drosophila have identified novel genes with conserved protein functions relevant to Cu homeostasis in humans. This review focuses on our current understanding of Cu uptake, distribution and export in Drosophila and the implications for mammals.

Reward modulation of hippocampal subfield activation during successful associative encoding and retrieval

PubMed Central

Wolosin, Sasha M.; Zeithamova, Dagmar; Preston, Alison R.

2012-01-01

Emerging evidence suggests that motivation enhances episodic memory formation through interactions between medial temporal lobe (MTL) structures and dopaminergic midbrain. In addition, recent theories propose that motivation specifically facilitates hippocampal associative binding processes, resulting in more detailed memories that are readily reinstated from partial input. Here, we used high-resolution functional magnetic resonance imaging to determine how motivation influences associative encoding and retrieval processes within human MTL subregions and dopaminergic midbrain. Participants intentionally encoded object associations under varying conditions of reward and performed a retrieval task during which studied associations were cued from partial input. Behaviorally, cued recall performance was superior for high-value relative to low-value associations; however, participants differed in the degree to which rewards influenced memory. The magnitude of behavioral reward modulation was associated with reward-related activation changes in dentate gyrus/CA2,3 during encoding and enhanced functional connectivity between dentate gyrus/CA2,3 and dopaminergic midbrain during both the encoding and retrieval phases of the task. These findings suggests that within the hippocampus, reward-based motivation specifically enhances dentate gyrus/CA2,3 associative encoding mechanisms through interactions with dopaminergic midbrain. Furthermore, within parahippocampal cortex and dopaminergic midbrain regions, activation associated with successful memory formation was modulated by reward across the group. During the retrieval phase, we also observed enhanced activation in hippocampus and dopaminergic midbrain for high-value associations that occurred in the absence of any explicit cues to reward. Collectively, these findings shed light on fundamental mechanisms through which reward impacts associative memory formation and retrieval through facilitation of MTL and VTA/SN processing. PMID:22524296

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol: Influence of Reaction Temperature and Feedstock.

PubMed

Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

2017-11-06

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while char-forming reactions become significant at high reaction temperature (>380 °C). At preferred intermediate temperatures (300-340 °C), char-forming reactions are effectively suppressed by alkylation and Guerbet and esterification reactions. This shifts the reaction toward depolymerization, explaining high monomeric aromatics yield. Carbon-14 dating analysis of the lignin residue revealed that a substantial amount of the carbon in the lignin residue originates from reactions of lignin with ethanol. Recycling tests show that the activity of the regenerated catalyst was strongly decreased due to a loss of basic sites due to hydrolysis of the MgO function and a loss of surface area due to spinel oxide formation of the Cu and Al components. The utility of this one-step approach for upgrading woody biomass was also demonstrated. An important observation is that conversion of the native lignin contained in the lignocellulosic matrix is much easier than the conversion of technical lignin.

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol: Influence of Reaction Temperature and Feedstock

PubMed Central

2017-01-01

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200–420 °C) on the product distribution is investigated. At low temperature (200–250 °C), recondensation is dominant, while char-forming reactions become significant at high reaction temperature (>380 °C). At preferred intermediate temperatures (300–340 °C), char-forming reactions are effectively suppressed by alkylation and Guerbet and esterification reactions. This shifts the reaction toward depolymerization, explaining high monomeric aromatics yield. Carbon-14 dating analysis of the lignin residue revealed that a substantial amount of the carbon in the lignin residue originates from reactions of lignin with ethanol. Recycling tests show that the activity of the regenerated catalyst was strongly decreased due to a loss of basic sites due to hydrolysis of the MgO function and a loss of surface area due to spinel oxide formation of the Cu and Al components. The utility of this one-step approach for upgrading woody biomass was also demonstrated. An important observation is that conversion of the native lignin contained in the lignocellulosic matrix is much easier than the conversion of technical lignin. PMID:29142789

Oxidative stress modulates the expression of genes involved in cell survival in ΔF508 cystic fibrosis airway epithelial cells.

PubMed

Voisin, Grégory; Bouvet, Guillaume F; Legendre, Pierre; Dagenais, André; Massé, Chantal; Berthiaume, Yves

2014-09-01

Although cystic fibrosis (CF) pathophysiology is explained by a defect in CF transmembrane conductance regulator (CFTR) protein, the broad spectrum of disease severity is the consequence of environmental and genetic factors. Among them, oxidative stress has been demonstrated to play an important role in the evolution of this disease, with susceptibility to oxidative damage, decline of pulmonary function, and impaired lung antioxidant defense. Although oxidative stress has been implicated in the regulation of inflammation, its molecular outcomes in CF cells remain to be evaluated. To address the question, we compared the gene expression profile in NuLi-1 cells with wild-type CFTR and CuFi-1 cells homozygous for ΔF508 mutation cultured at air-liquid interface. We analyzed the transcriptomic response of these cell lines with microarray technology, under basal culture conditions and after 24 h oxidative stress induced by 15 μM 2,3-dimethoxy-1,4-naphtoquinone. In the absence of oxidative conditions, CuFi-1 gene profiling showed typical dysregulated inflammatory responses compared with NuLi-1. In the presence of oxidative conditions, the transcriptome of CuFi-1 cells reflected apoptotic transcript modulation. These results were confirmed in the CFBE41o- and corrCFBE41o- cell lines as well as in primary culture of human CF airway epithelial cells. Altogether, our data point to the influence of oxidative stress on cell survival functions in CF and identify several genes that could be implicated in the inflammation response observed in CF patients. Copyright © 2014 the American Physiological Society.

Preparation of bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes for hydrolytic dehydrogenation of ammonia borane

NASA Astrophysics Data System (ADS)

Liu, Yang; Zhang, Jun; Guan, Huijuan; Zhao, Yafei; Yang, Jing-He; Zhang, Bing

2018-01-01

In present work, we prepared the bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes (Cu-Co/PDDA-HNTs) by a deposition-reduction technique at room temperature. The analysis of XRD, SEM, TEM, HAADF-STEM and XPS were employed to systematically investigate the morphology, particle size, structure and surface properties of the nanocomposite. The results reveal that the PDDA coating with thickness of ∼15 nm could be formed on the surface of HNTs, and the existence of PDDA is beneficial to deposit Cu and Co nanoparticles (NPs) with high dispersibility on the surface. While the cost-effective nanocomposite was used for the hydrolytic dehydrogenation of ammonia-borane (NH3BH3), the nanocatalyst showed extraordinary catalytic properties with high total turnover frequency of 30.8 molH2/(molmetal min), low activation energy of 35.15 kJ mol-1 and high recycling stability (>90% conversion at 10th reuse). These results indicate that the bimetallic Cu-Co nanocatalysts on PDDA functionalized HNTs have particular potential for application in release hydrogen process.

Optoelectronic and Defect Properties in Earth Abundant Photovoltaic Materials: First-principle Calculations

NASA Astrophysics Data System (ADS)

Shi, Tingting

In this dissertation, a series of earth-abundant photovoltaic materials including lead halide perovskites, copper based compounds, and silicon are investigated via density functional theory (DFT). Firstly, we study the unique optoelectronic properties of perovskite CH3NH3PbI3 and CH3NH3PbBr 3. First-principle calculations show that CH3NH3PbI 3 perovskite solar cells exhibit remarkable optoelectronic properties that account for the high open circuit voltage (Voc) and long electron-hole diffusion lengths. Our results reveal that for intrinsic doping, dominant point defects produce only shallow levels. Therefore lead halide perovskites are expected to exhibit intrinsic low non-radiative recombination rates. The conductivity of perovskites can be tuned from p-type to n-type by controlling the growth conditions. For extrinsic defects, the p-type perovskites can be achieved by doping group-IA, -IB, or -VIA elements, such as Na, K, Rb, Cu, and O at I-rich growth conditions. We further show that despite a large band gap of 2.2 eV, the dominant defects in CH3 NH3PbBr3 also create only shallow levels. The photovoltaic properties of CH3NH3PbBr3 - based perovskite absorbers can be tuned via defect engineering. Highly conductive p-type CH3NH3PbBr3 can be synthesized under Br-rich growth conditions. Such CH3NH3PbBr 3 may be potential low-cost hole transporting materials for lead halide perovskite solar cells. All these unique defect properties of perovskites are largely due to the strong Pb lone-pair s orbital and I p (Br p) orbital antibonding coupling and the high ionicity of CH3NH3PbX3 (X=I, Br). Secondly, we study the optoelectronic properties of Cu-V-VI earth abundant compounds. These low cost thin films may have the good electronic and optical properties. We have studied the structural, electronic and optical properties of Cu3-V-VI4 compounds. After testing four different crystal structures, enargite, wurtzite-PMCA, famatinite and zinc-blend-PMCA, we find that Cu3PS4 and Cu3PSe4 prefer energetically the enargite structure, whereas, other compounds favor the famatinite structure. Among the compounds and structures considered, enargite Cu3PSe4, and famatinite Cu3AsS4, are suitable for single junction solar cell applications due to bandgaps of 1.32 eV and 1.15 eV, respectively. Furthermore, CuSbS2 are also studied by density functional theory and HSE06 hybrid functional. The chalcostibite CuSbS2 has an indirect band gap of 1.85 eV, whereas the chalcogenide Cu3SbS4 has a direct band gap of 0.89 eV. We find that the large difference on band gaps is mainly attributed to the different Sb charge states. We further predict that the Sb charge states will affect the defect physics. Particularly, the Sb lone pair s orbitals in CuSbS 2 have strong influence on the formation energies of Sb-related defects. Lastly, we have studied the atomic structure and electronic properties of aluminum (Al)-related defect complexes in silicon. We find a unique stable complex configuration consisting of an Ali and an oxygen dimer, Ali-2Oi, which introduces deep levels in the band gap of Si. The formation energies of the Ali-2Oi complexes could be lower than that of individual Ali atoms under oxygen-rich conditions. The formation of Ali-2Oi complexes may explain the experimental observation that the coexistence of Al and O results in reduced carrier lifetime in Si wafers.

Galvanic corrosion behaviors of Cu connected to Au on a printed circuit board in ammonia solution

NASA Astrophysics Data System (ADS)

Oh, SeKwon; Kim, YoungJun; Jung, KiMin; Park, MiSeok; Shon, MinYoung; Kwon, HyukSang

2018-01-01

During etching treatments of printed circuit board (PCB) with ammnioa solution, galvanic corrosion occurs between electrically connected gold and copper, and resulting in unexpected over-etching problems. Herein, we determine corrosion of galvanic coupled Cu to Au quantitatively in ammonia solutions, and evaluate factors influencing corrosion of galvanic coupled Cu to Au (i.e., area ratio of anode to cathode and stirring speed). The difference of the corrosion rate (Δi = icouple, (Cu-Au)-icorr, Cu) of Cu connected to Au (117 μA/cm2) and of single Cu (86 μA/cm2) infers the amount of over-etching of Cu resulting from galvanic corrosion in ammonia solution (Δi = 0.31 μA/cm2). As the stirring speed increases from 0 to 400 rpm, the corrosion rate of galvanic coupled Cu to Au increases from 36 to 191 μA/cm2. Furthermore, we confirm that an increase in the area ratio (Au/Cu) from 0.5 to 25 results in a higher rate of corrosion of Cu connected to Au. The corrosion rate of galvanic coupled Cu to Au is approximately 20 times higher when the area ratio of Au to Cu is 25 (1360 μA/cm2) than when the ratio is 0.5 (67 μA/cm2).

Direct synthesis of carbon nanotubes using Cu-Sn catalyst on Cu substrates and their corrosion behavior in 0.6 M NaCl solution

NASA Astrophysics Data System (ADS)

Jeong, Namjo; Jwa, Eunjin; Kim, Chansoo; Choi, Ji Yeon; Nam, Joo-youn; Park, Soon-chul; Jang, Moon-seok

2017-11-01

We report the high-yield and large-area synthesis of a spaghetti-like carbon nanotubes (CNTs) on macroscopic Cu substrates (foil and foam) using a Cu-Sn alloy catalyst. In addition, we investigate the corrosion properties of the as-synthesized CNT/Cu foil system in 0.6 M NaCl solution. Electrochemical analysis showed that the corrosion resistance of the CNT/Cu foil system improved by a factor of ∼100 compared to the as-received Cu foil. Thus, it is concluded that a dense network of CNT was uniformly coated on the Cu foil and this coating functioned as an efficient barrier to corrosion under simulated seawater conditions.

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

NASA Astrophysics Data System (ADS)

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

2014-02-01

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

Pd/Cu-Oxide Nanoconjugate at Zeolite-Y Crystallite Crafting the Mesoporous Channels for Selective Oxidation of Benzyl-Alcohols.

PubMed

Sharma, Mukesh; Das, Biraj; Sharma, Mitu; Deka, Biplab K; Park, Young-Bin; Bhargava, Suresh K; Bania, Kusum K

2017-10-11

Solid-state grinding of palladium and copper salts allowed the growth of palladium/copper oxide interface at the zeolite-Y surface. The hybrid nanostructured material was used as reusable heterogeneous catalyst for selective oxidation of various benzyl alcohols. The large surface area provided by the zeolite-Y matrix highly influenced the catalytic activity, as well as the recyclability of the synthesized catalyst. Impregnation of PdO-CuO nanoparticles on zeolite crystallite leads to the generation of mesoporous channel that probably prevented the leaching of the metal-oxide nanoparticles and endorsed high mass transfer. Formation of mesoporous channel at the external surface of zeolite-Y was evident from transmission electron microscopy and surface area analysis. PdO-CuO nanoparticles were found to be within the range of 2-5 nm. The surface area of PdO-CuO-Y catalyst was found to be much lower than parent zeolite-Y. The decrease in surface area as well as the presence of hysteresis loop in the N 2 -adsoprtion isotherm further suggested successful encapsulation of PdO-CuO nanoparticles via the mesoporous channel formation. The high positive shifting in binding energy in both Pd and Cu was attributed to the influence of zeolite-Y framework on lattice contraction of metal oxides via confinement effect. PdO-CuO-Y catalyst was found to oxidize benzyl alcohol with 99% selectivity. On subjecting to microwave irradiation the same oxidation reaction was found to occur at ambient condition giving same conversion and selectivity.

Divided Attention and Processes Underlying Sense of Agency

PubMed Central

Wen, Wen; Yamashita, Atsushi; Asama, Hajime

2016-01-01

Sense of agency refers to the subjective feeling of controlling events through one’s behavior or will. Sense of agency results from matching predictions of one’s own actions with actual feedback regarding the action. Furthermore, when an action involves a cued goal, performance-based inference contributes to sense of agency. That is, if people achieve their goal, they would believe themselves to be in control. Previous studies have shown that both action-effect comparison and performance-based inference contribute to sense of agency; however, the dominance of one process over the other may shift based on task conditions such as the presence or absence of specific goals. In this study, we examined the influence of divided attention on these two processes underlying sense of agency in two conditions. In the experimental task, participants continuously controlled a moving dot for 10 s while maintaining a string of three or seven digits in working memory. We found that when there was no cued goal (no-cued-goal condition), sense of agency was impaired by high cognitive load. Contrastingly, when participants controlled the dot based on a cued goal (cued-goal-directed condition), their sense of agency was lower than in the no-cued-goal condition and was not affected by cognitive load. The results suggest that the action-effect comparison process underlying sense of agency requires attention. On the other hand, the weaker influence of divided attention in the cued-goal-directed condition could be attributed to the dominance of performance-based inference, which is probably automatic. PMID:26858680

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

In vitro release of cupric ion from intrauterine devices: influence of frame, shape, copper surface area and indomethacin.

PubMed

Zhang, Shuangshuang; Li, Ying; Yu, Panpan; Chen, Tong; Zhou, Weisai; Zhang, Wenli; Liu, Jianping

2015-02-01

The release of cupric ion from copper intrauterine device (Cu-IUD) in human uterus is essential for contraception. However, excessive cupric ion will cause cytotoxic effect. In this paper, we investigated the influence of device characteristics (frame, copper surface area, shape, copper type and indomethacin) on copper release for the efficacy and adverse effects vary with IUD types which may correlate to their different release behaviors. Nine types of Cu-IUDs were selected and incubated in simulated uterine fluid. They were paired for comparison based on the device properties and the release of cupric ion was determined by flame atomic absorption spectrometer for about 160 days. The result showed that there was a burst release during the first month and the release rate tends to slow down and become steady afterwards. In addition, the copper release was mainly influenced by frame, indomethacin and copper type (copper wire and copper sleeve) while the shape variation had little effect on copper release throughout the experiment. Moreover, the influence of copper surface area was only noticeable during the first month. These findings were seldom reported before and may provide some useful information for the design of Cu-IUDs.

High heating rate decomposition dynamics of copper oxide by nanocalorimetry-coupled time-of-flight mass spectrometry

NASA Astrophysics Data System (ADS)

Yi, Feng; DeLisio, Jeffery B.; Nguyen, Nam; Zachariah, Michael R.; LaVan, David A.

2017-12-01

The thermodynamics and evolved gases were measured during the rapid decomposition of copper oxide (CuO) thin film at rates exceeding 100,000 K/s. CuO decomposes to release oxygen when heated and serves as an oxidizer in reactive composites and chemical looping combustion. Other instruments have shown either one or two decomposition steps during heating. We have confirmed that CuO decomposes by two steps at both slower and higher heating rates. The decomposition path influences the reaction course in reactive Al/CuO/Al composites, and full understanding is important in designing reactive mixtures and other new reactive materials.

Surface states and annihilation characteristics of positrons trapped at the oxidized Cu(100) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Weiss, A. H.

2013-06-01

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Oxidation of the Cu(100) surface has been studied by performing an ab-initio investigation of the stability and electronic structure of the Cu(100) missing row reconstructed surface at various on-surface and subsurface oxygen coverages ranging from 0.5 to 1.5 monolayers using density functional theory (DFT). All studied structures have been found to be energetically more favorable as compared to structures formed by purely on-surface oxygen adsorption. The observed decrease in the positron work function when oxygen atoms occupy on-surface and subsurface sites has been attributed to a significant charge redistribution within the first two layers, buckling effects within each layer and an interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of the surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). The results presented provide an explanation for the changes observed in the probability of annihilation of surface trapped positrons with Cu 3p core-level electrons as a function of annealing temperature.

Hydration of copper(II): new insights from density functional theory and the COSMO solvation model.

PubMed

Bryantsev, Vyacheslav S; Diallo, Mamadou S; van Duin, Adri C T; Goddard, William A

2008-09-25

The hydrated structure of the Cu(II) ion has been a subject of ongoing debate in the literature. In this article, we use density functional theory (B3LYP) and the COSMO continuum solvent model to characterize the structure and stability of [Cu(H2O)n](2+) clusters as a function of coordination number (4, 5, and 6) and cluster size (n = 4-18). We find that the most thermodynamically favored Cu(II) complexes in the gas phase have a very open four-coordinate structure. They are formed from a stable square-planar [Cu(H2O)8](2+) core stabilized by an unpaired electron in the Cu(II) ion d(x(2)-y(2)) orbital. This is consistent with cluster geometries suggested by recent mass-spectrometric experiments. In the aqueous phase, we find that the more compact five-coordinate square-pyramidal geometry is more stable than either the four-coordinate or six-coordinate clusters in agreement with recent combined EXAFS and XANES studies of aqueous solutions of Cu(II). However, a small energetic difference (approximately 1.4 kcal/mol) between the five- and six-coordinate models with two full hydration shells around the metal ion suggests that both forms may coexist in solution.

Bifunctional silica nanospheres with 3-aminopropyl and phenyl groups. Synthesis approach and prospects of their applications

NASA Astrophysics Data System (ADS)

Kotsyuda, Sofiya S.; Tomina, Veronika V.; Zub, Yuriy L.; Furtat, Iryna M.; Lebed, Anastasia P.; Vaclavikova, Miroslava; Melnyk, Inna V.

2017-10-01

Spherical silica particles with bifunctional (tbnd Si(CH2)3NH2/tbnd SiC6H5) surface layers were synthesized by the Stöber method using ternary alkoxysilanes systems. The influence of the synthesis conditions, such as temperature and stirring time on the process of nanoparticles formation was studied. The presence of introduced functional groups was confirmed by FTIR. The composition of the surface layers examined by elemental analysis and acid-base titration was shown to be independent from the synthesis temperature. However, the size of the obtained particles depends on the synthesis temperature and, according to photon cross-correlation spectroscopy, can be varied from 50 to 846 nm. The variation of electric charges of N-functional groups was disclosed in obtained nanospheres and attributed to different surface location of these groups and their surrounding with other groups. The sorption of Cu(II) ions by functionalized silicas depends on the concentration of amino groups, which correlates with the isoelectric point values (determined to vary from 8.26 to 9.21). Bifunctional nanoparticles adsorb 99.0 mg/g of methylene blue, compared with 48.0 mg/g by silica sample with only amino groups. The nanospheres, both with and without adsorbed Cu2+, demonstrate reasonable antibacterial activity against S. aureus ATCC 25923, depending on particle concentration in water suspension.

A kinetic study on the formation of poly(4 aminodiphenylamine)/copper nanocomposite using UV-visible spectroscopy.

PubMed

Starlet Thanjam, I; Francklin Philips, M; Manisankar, P; Lee, Kwang-Pill; Gopalan, A

2013-12-01

The course of the reaction between copper sulfate (CuSO4) and 4-aminodiphenylamine (4ADPA) was monitored by UV-visible spectroscopy in p-toluene sulfonic acid (p-TSA). Formation of poly(4-aminodiphenylamine)/copper nanoparticle composite (P4ADPA/CuNC) was witnessed through the steady increase in absorbance at 410, 580 and >700 nm. The absorbance at 410 nm as well as >700 nm are correlated to the amount of P4ADPA/CuNC formation and was subsequently used to determine the rate of formation of P4ADPA/CuNC (RP4ADPA/CuNC) at any time during the course of the reaction. RP4ADPA/CuNC shows a first-order dependence on [4ADPA] and a half-order dependence on [CuSO4]. A kinetic rate expression was established between RP4ADPA/CuNC and experimental parameters such as [4ADPA] and [CuSO4]. The rate constant for the formation of P4ADPA/CuNC was 8.98 × 10(-3) mol(-0.5) l(0.5) s(-1). Field emission scanning electron and transmission electron micrographs revealed that the morphology of the P4ADPA/CuNC was influenced by the reaction conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

Solid phase selective separation and preconcentration of Cu(II) by Cu(II)-imprinted polymethacrylic microbeads.

PubMed

Dakova, Ivanka; Karadjova, Irina; Ivanov, Ivo; Georgieva, Ventsislava; Evtimova, Bisera; Georgiev, George

2007-02-12

Ion-imprinted polymer (IIP) particles are prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as crosslinking agent and 2,2'-azo-bis-isobutyronitrile as initiator in the presence of Cu(II), a Cu(II)-4-(2-pyridylazo)resorcinol (Cu(II)-PAR) complex, and PAR only. A batch procedure is used for the determination of the characteristics of the Cu(II) solid phase extraction from the IIP produced. The results obtained show that the Cu(II)-PAR IIP has the greatest adsorption capacity (37.4 micromol g(-1) of dry copolymer) among the IIPs investigated. The optimal pH value for the quantitative preconcentration is 7, and full desorption is achieved by 1 M HNO(3). The selectivity coefficients (S(Cu/Me)) for Me=Ni(II), Co(II) are 45.0 and 38.5, respectively. It is established that Cu(II)-PAR IIPs can be used repeatedly without a considerable adsorption capacity loss. The determination of Cu(II) ions in seawater shows that the interfering matrix does not influence the preconcentration and selectivity values of the Cu(II)-PAR IIPs. The detection and quantification limits are 0.001 micromol L(-1) (3sigma) and 0.003 micromol L(-1) (6sigma), respectively.

Structural properties of CuAu nanoparticles with different type. Molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Chepkasov, I. V.; Baidyshev, V. S.; Baev, A. Y.

2018-05-01

The paper is devoted to the thermal stability of a CuAu nanoparticles structure (D=5 nm) of various type (binary alloy, core-shell, "Janus" type) and of various percentage of copper atoms. The simulation was carried out with molecular dynamics, using the embedded atom potential. The authors defined the most preferable structural options from the standpoint of thermodynamics, as well as studied in detail the influence of different temperatures on the structural stability of CuAu nanoparticles.

Influence of gravity level and interfacial energies on dispersion-forming tendencies in hypermonotectic Cu-Pb-Al alloys

NASA Technical Reports Server (NTRS)

Andrews, J. B.; Curreri, P. A.; Sandlin, A. C.

1988-01-01

Results on the nondirectional solidification of several hypermonotectic Cu-Pb-Al alloys were obtained aboard NASA's KC-135 zero-gravity aircraft in order to determine the influence of interfacial energies and gravity levels on dispersion-forming tendencies. The Al content was systematially varied in the alloys. The dispersion-forming ability is correlated with gravity level during solidification, the interfacial energy between the immiscible phases, and the tendency for the minority immiscible phase to wet the walls of the crucible.

Dispersive charge density wave excitations in Bi 2Sr 2CaCu 2O 8+δ [Dispersive charge density wave excitations and temperature dependent commensuration in Bi 2Sr 2CaCu 2O 8+δ

DOE PAGES

Chaix, L.; Ghiringhelli, G.; Peng, Y. Y.; ...

2017-06-12

Experimental evidence on high-T c cuprates reveals ubiquitous charge density wave (CDW) modulations, which coexist with superconductivity. Although the CDW had been predicted by theory, important questions remain about the extent to which the CDW influences lattice and charge degrees of freedom and its characteristics as functions of doping and temperature. These questions are intimately connected to the origin of the CDW and its relation to the mysterious cuprate pseudogap. We use ultrahigh-resolution resonant inelastic X-ray scattering to reveal new CDW character in underdoped Bi 2.2Sr 1.8Ca 0.8Dy 0.2Cu 2O 8+δ. At low temperature, we observe dispersive excitations from anmore » incommensurate CDW that induces anomalously enhanced phonon intensity, unseen using other techniques. Furthermore, near the pseudogap temperature T*, the CDW persists, but the associated excitations significantly weaken with an indication of CDW wavevector shift. The dispersive CDW excitations, phonon anomaly, and analysis of the CDW wavevector provide a comprehensive momentum-space picture of complex CDW behaviour and point to a closer relationship with the pseudogap state.« less

Assessment of the effects of glutamic acid decarboxylase antibodies and trace elements on cognitive performance in older adults.

PubMed

Alghadir, Ahmad H; Gabr, Sami A; Al-Eisa, Einas S

2015-01-01

Homeostatic imbalance of trace elements such as iron (Fe), copper (Cu), and zinc (Zn) demonstrated adverse effects on brain function among older adults. The present study aimed to investigate the effects of trace elements and the presence of anti-glutamic acid decarboxylase antibodies (GADAs) in human cognitive abilities among healthy older adults. A total of 100 healthy subjects (65 males, 35 females; age range; 64-96 years) were recruited for this study. Based on Loewenstein Occupational Therapy Cognitive Assessment (LOTCA) score, the participants were classified according to cognitive performance into normal (n=45), moderate (n=30), and severe (n=25). Cognitive functioning, leisure-time physical activity (LTPA), serum trace elements - Fe, Cu, Zn, Zn/Cu, and GADAs were assessed using LOTCA battery, pre-validated physical activity (PA) questionnaire, atomic absorption, and immunoassay techniques, respectively. Approximately 45% of the study population (n=45) had normal distribution of cognitive function and 55% of the study population (n=55) had abnormal cognitive function; they were classified into moderate (score 62-92) and severe (score 31-62). There was a significant reduction in the level of Zn and Zn/Cu ratio along with an increase in the level of Fe, Cu, and anti-GADAs in subjects of severe (P=0.01) and moderate (P=0.01) cognitive performance. LOTCA-cognitive scores correlated positively with sex, HbA(1c), Fe, Cu, Zn, and Zn/Cu ratio, and negatively with age, PA, body mass index, and anti-GADAs. Significant inter-correlation was reported between serum trace element concentrations and anti-GADAs which suggest producing a cognitive decline via oxidative and neural damage mechanism. This study found significant associations among trace elements, anti-GADAs, and cognitive function in older adults. The homeostatic balance of trace elements should be recommended among older adults for better cognitive performance.

Child maltreatment, callous-unemotional traits, and defensive responding in high-risk children: An investigation of emotion-modulated startle response.

PubMed

Dackis, Melissa N; Rogosch, Fred A; Cicchetti, Dante

2015-11-01

Child maltreatment is associated with disruptions in physiological arousal, emotion regulation, and defensive responses to cues of threat and distress, as well as increased risk for callous unemotional (CU) traits and externalizing behavior. Developmental models of CU traits have focused on biological and genetic risk factors that contribute to hypoarousal and antisocial behavior, but have focused less on environmental influences (Blair, 2004; Daversa, 2010; Hare, Frazell, & Cox, 1978; Krueger, 2000; Shirtcliff et al., 2009; Viding, Fontaine, & McCrory, 2012). The aim of the present investigation was to measure the independent and combined effects of child maltreatment and high CU traits on emotion-modulated startle response in children. Participants consisted of 132 low-income maltreated (n = 60) and nonmaltreated (n = 72) children between 8 and 12 years old who attended a summer camp program. Acoustic startle response (ASR) was elicited in response to a 110-dB 50-ms probe while children viewed a slideshow of pleasant, neutral, and unpleasant IAPS images. Maltreatment status was assessed through examination of Department of Human Services records. CU traits were measured using counselor reports from the Inventory of Callous and Unemotional Traits (Frick, 2004), and conduct problems were measured using counselor and child self-report. We found no significant differences in emotion-modulated startle in the overall sample. However, significant differences in ASR by maltreatment status, maltreatment subtype, and level of CU traits were apparent. Results indicated differential physiological responses for maltreated and nonmaltreated children based on CU traits, including a pathway of hypoarousal for nonmaltreated/high CU children that differed markedly from a more normative physiological trajectory for maltreated/high CU children. Further, we found heightened ASR for emotionally and physically neglected children with high CU and elevated antisocial behavior in these children. Results provide further support for differential trajectories by which experience and biology may influence the development of antisocial behavior in youth and highlight potential avenues for intervention.

Child Maltreatment, Callous-Unemotional Traits, and Defensive Responding In High-Risk Children: An Investigation of Emotion-Modulated Startle Response

PubMed Central

Dackis, Melissa N.; Rogosch, Fred A.; Cicchetti, Dante

2015-01-01

Child maltreatment is associated with disruptions in physiological arousal, emotion regulation, and defensive responses to cues of threat and distress, as well as increased risk for callous unemotional (CU) traits and externalizing behavior. Developmental models of callous unemotional (CU) traits have focused on biological and genetic risk factors that contribute to hypoarousal and antisocial behavior, but have focused less on environmental influences (Blair, 2004; Daversa, 2010; Hare, Frazell, & Cox, 1978; Krueger, 2000; Shirtcliff et al., 2009; Viding, Fontaine, & McCrory, 2012). The aim of the present investigation was to measure the independent and combined effects of child maltreatment and high CU trait on emotion-modulated startle (EMS) response in children. Participants consisted of 132 low-income maltreated (n = 60) and nonmaltreated (n = 72) children between 8–12 years old who attended a summer camp program. Acoustic startle response (ASR) was elicited in response to a 110-dB 50-ms probe while children viewed a slideshow of pleasant, neutral, and unpleasant IAPS images. Maltreatment status was assessed through examination of Department of Human Services records. CU traits were measured using counselor reports from the Inventory of Callous and Unemotional Traits (ICU; Frick, 2004), and conduct problems were measured using counselor and child self-report. We found no significant differences in emotion-modulated startle in the overall sample. However, significant differences in ASR by maltreatment status, maltreatment subtype, and level of CU traits were apparent. Results indicated differential physiological responses for maltreated and nonmaltreated children based on CU traits, including a pathway of hypoarousal for nonmaltreated/high CU children that differed markedly from a more normative physiological trajectory for maltreated/high CU children. Further, we found heightened ASR for emotionally and physically neglected children with high CU and elevated antisocial behavior in these children. Results provide further support for differential trajectories by which experience and biology may influence the development of antisocial behavior in youth and highlight potential avenues for intervention. PMID:26535942

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Robust and Stable Cu Nanowire@Graphene Core-Shell Aerogels for Ultraeffective Electromagnetic Interference Shielding.

PubMed

Wu, Shiting; Zou, Mingchu; Li, Zhencheng; Chen, Daqin; Zhang, Hui; Yuan, Yongjun; Pei, Yongmao; Cao, Anyuan

2018-06-01

Cu nanowires (CuNWs) are considered as a promising candidate to develop high performance metal aerogels, yet the construction of robust and stable 3D porous structures remains challenging which severely limits their practical applications. Here, graphene-hybridized CuNW (CuNW@G) core-shell aerogels are fabricated by introducing a conformal polymeric coating and in situ transforming it into multilayered graphene seamlessly wrapped around individual CuNWs through a mild thermal annealing process. The existence of the outer graphene shell reinforces the 3D bulk structure and significantly slows down the oxidation process of CuNWs, resulting in improved mechanical property and highly stable electrical conductivity. When applied in electromagnetic interference shielding, the CuNW@G core-shell aerogels exhibit an average effectiveness of ≈52.5 dB over a wide range (from 8.2 to 18 GHz) with negligible degradation under ambient conditions for 40 d. Mechanism analysis reveals that the graphene shell with functional groups enables dual reflections on the core-shell and a multiple dielectric relaxation process, leading to enhanced dielectric loss and energy dissipation within the core-shell aerogels. The flexible core-shell-structured CuNW@G aerogels, with superior mechanical robustness and electrical stability, have potential applications in many areas such as advanced energy devices and functional composites. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical Investigation of Calculating Temperatures in the Combining Zone of Cu/Fe Composite Plate Jointed by Explosive Welding

NASA Astrophysics Data System (ADS)

Qu, Y. D.; Zhang, W. J.; Kong, X. Q.; Zhao, X.

2016-03-01

The heat-transfer behavior of the interface of Flyer plate (or Base Plate) has great influence on the microcosmic structures, stress distributions, and interface distortion of the welded interface of composite plates by explosive welding. In this paper, the temperature distributions in the combing zone are studied for the case of Cu/Fe composite plate jointed by explosive welding near the lower limit of explosive welding. The results show that Flyer plate (Cu plate) and Base Plate (Fe plate) firstly almost have the same melting rate in the explosive welding process. Then, the melting rate of Cu plate becomes higher than that of Fe plate. Finally, the melt thicknesses of Cu plate and Fe plate trend to be different constants, respectively. Meanwhile, the melting layer of Cu plate is thicker than that of Fe plate. The research could supply some theoretical foundations for calculating the temperature distribution and optimizing the explosive welding parameters of Cu/Fe composite plate to some extent.

Influence of the ultrasound-assisted synthesis of Cu-BTC metal-organic frameworks nanoparticles on uptake and release properties of rifampicin.

PubMed

Abbasi, Amir Reza; Rizvandi, Maryam

2018-01-01

In this work, we study uptake and release properties of rifampicin (denoted henceforth as Rif) from ultrasound-assisted synthesis Cu-BTC nanoparticles in comparison with bulk Cu-BTC and activated carbon. To explore the absorption ability of the Cu-BTC to Rif, fresh sample of Cu-BTC was immersed in an aqueous solution of Rif and were monitored in real time with UV/vis spectroscopy. Results show that the adsorbed quantity of Rif over nano Cu-BTC (denoted henceforth as I) is much higher than those over a bulk Cu-BTC (denoted henceforth as II) and activated carbon. In compound I and all of the nano-MOFs the channel length is decreased so that the amount of adsorption is increased a little. The samples were characterized with X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and UV/vis spectroscopy. Copyright © 2017 Elsevier B.V. All rights reserved.

Cu-Au Alloys Using Monte Carlo Simulations and the BFS Method for Alloys

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Good, Brian; Ferrante, John

1996-01-01

Semi empirical methods have shown considerable promise in aiding in the calculation of many properties of materials. Materials used in engineering applications have defects that occur for various reasons including processing. In this work we present the first application of the BFS method for alloys to describe some aspects of microstructure due to processing for the Cu-Au system (Cu-Au, CuAu3, and Cu3Au). We use finite temperature Monte Carlo calculations, in order to show the influence of 'heat treatment' in the low-temperature phase of the alloy. Although relatively simple, it has enough features that could be used as a first test of the reliability of the technique. The main questions to be answered in this work relate to the existence of low temperature ordered structures for specific concentrations, for example, the ability to distinguish between rather similar phases for equiatomic alloys (CuAu I and CuAu II, the latter characterized by an antiphase boundary separating two identical phases).

The YBa2Cu3O7- anomalous second peak and irreversible magnetic field in the magnetization hysteresis cycles

NASA Astrophysics Data System (ADS)

Taoufik, A.; Ramzi, A.; Senoussi, S.; Labrag, A.

2004-05-01

The flux jumps, the second peak and the irreversible magnetic field in the magnetization hysteresis cycles have been investigated in the high temperature superconductor YBa2Cu3O7- single crystals. These cycles were obtained for different temperature values, the applied magnetic fields up to 6 T and the angle between the applied magnetic field and c-axis. The magnetization curves exhibit a remarkable second peak fishtail, this second peak was not observed for the low temperature, but we observed the flux jumps saw tooth. The temperature dependence of the irreversible magnetic field, Hirr, for the applied magnetic field perpendicular to the ab planes is given by an extended expression, Hirr α (1-T/Tc )α, where α is a constant, the Abrikosov flux dynamics can explain this behavior. The Hirr as a function of has been strongly influenced by the flux pinning and the thermally assisted flux motion.

A study of ignition of metal impregnated carbons: the influence of oxygen content in the activated carbon matrix.

PubMed

van der Merwe, M M; Bandosz, T J

2005-02-01

A study of the reason for the early ignition of coconut-based impregnated carbon in comparison with the peat-based impregnated carbon was conducted. The surface features of carbons were evaluated using various physicochemical methods. The metal analysis of the initial carbon indicated that the content of potassium was higher in the coconut-based carbon. The surface functional group analysis revealed the presence of similar surface species; however, the peat-based carbon was more acidic in its chemical nature. Since the oxygen content was higher in the peat-based carbon, the early ignition of the coconut-based material was attributed to its higher affinity to chemisorb oxygen, which leads to exothermic effects. This conclusion was confirmed by performing oxidation of coconut-based carbon prior to impregnation. This process increased the ignition temperature for Cu/Cr impregnated coconut-based material from 186 to 289 degrees C and for the Cu/Zn/Mo impregnated carbon from 235 to 324 degrees C.

Fear-conditioning mechanisms associated with trait vulnerability to anxiety in humans.

PubMed

Indovina, Iole; Robbins, Trevor W; Núñez-Elizalde, Anwar O; Dunn, Barnaby D; Bishop, Sonia J

2011-02-10

Investigations of fear conditioning in rodents and humans have illuminated the neural mechanisms underlying cued and contextual fear. A critical question is how personality dimensions such as trait anxiety act through these mechanisms to confer vulnerability to anxiety disorders, and whether humans' ability to overcome acquired fears depends on regulatory skills not characterized in animal models. In a neuroimaging study of fear conditioning in humans, we found evidence for two independent dimensions of neurocognitive function associated with trait vulnerability to anxiety. The first entailed increased amygdala responsivity to phasic fear cues. The second involved impoverished ventral prefrontal cortical (vPFC) recruitment to downregulate both cued and contextual fear prior to omission (extinction) of the aversive unconditioned stimulus. These two dimensions may contribute to symptomatology differences across anxiety disorders; the amygdala mechanism affecting the development of phobic fear and the frontal mechanism influencing the maintenance of both specific fears and generalized anxiety. Copyright © 2011 Elsevier Inc. All rights reserved.

Density-tunable lightweight polymer composites with dual-functional ability of efficient EMI shielding and heat dissipation.

PubMed

Lee, Seung Hwan; Yu, Seunggun; Shahzad, Faisal; Kim, Woo Nyon; Park, Cheolmin; Hong, Soon Man; Koo, Chong Min

2017-09-21

Lightweight dual-functional materials with high EMI shielding performance and thermal conductivity are of great importance in modern cutting-edge applications, such as mobile electronics, automotive, aerospace, and military. Unfortunately, a clear material solution has not emerged yet. Herein, we demonstrate a simple and effective way to fabricate lightweight metal-based polymer composites with dual-functional ability of excellent EMI shielding effectiveness and thermal conductivity using expandable polymer bead-templated Cu hollow beads. The low-density Cu hollow beads (ρ ∼ 0.44 g cm -3 ) were fabricated through electroless plating of Cu on the expanded polymer beads with ultralow density (ρ ∼ 0.02 g cm -3 ). The resulting composites that formed a continuous 3D Cu network with a very small Cu content (∼9.8 vol%) exhibited excellent EMI shielding (110.7 dB at 7 GHz) and thermal conductivity (7.0 W m -1 K -1 ) with isotropic features. Moreover, the densities of the composites are tunable from 1.28 to 0.59 g cm -3 in accordance with the purpose of their applications. To the best of our knowledge, the resulting composites are the best lightweight dual-functional materials with exceptionally high EMI SE and thermal conductivity performance among synthetic polymer composites.

Solid Phase Extraction of Trace Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) Ions in Beverages on Functionalized Polymer Microspheres Prior to Flame Atomic Absorption Spectrometric Determinations.

PubMed

Berber, Hale; Alpdogan, Güzin

2017-01-01

In this study, poly(glycidyl methacrylate-methyl methacrylate-divinylbenzene) was synthesized in the form of microspheres, and then functionalized by 2-aminobenzothiazole ligand. The sorption properties of these functionalized microspheres were investigated for separation, preconcentration and determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions using flame atomic absorption spectrometry. The optimum pH values for quantitative sorption were 2 - 4, 5 - 8, 6 - 8, 4 - 6, 2 - 6 and 2 - 3 for Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II), respectively, and also the highest sorption capacity of the functionalized microspheres was found to be for Cu(II) with the value of 1.87 mmol g -1 . The detection limits (3σ; N = 6) obtained for the studied metals in the optimal conditions were observed in the range of 0.26 - 2.20 μg L -1 . The proposed method was successfully applied to different beverage samples for the determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions, with the relative standard deviation of <3.7%.

Grafting of [(64)Cu]-TPPF20 porphyrin complex on Functionalized nano-porous MCM-41 silica as a potential cancer imaging agent.

PubMed

Fazaeli, Yousef; Feizi, Shahzad; Jalilian, Amir R; Hejrani, Ali

2016-06-01

Mesoporous silica, MCM-41, functionalized with 3-aminopropyltriethoxysilane (APTES) was investigated as a potential drug delivery system, using [(64)Cu]-5, 10, 15, 20-tetrakis penta fluorophenyl porphyrin complex. [(64)Cu]-TPPF20 complex was grafted on functionalized MCM-41. The product was characterized by paper chromatography, FTIR spectroscopy, low angle X-ray diffraction, CHN and TGA/DTA analyses and atomic force microscopy. The biological evaluations of the grafted complex, [(64)Cu]-TPPF20@NH2-MCM-41, were done in Fibrosarcoma tumor-bearing Sprague-Dawley rats using scarification studies and Sopha DST-XL Dual-Head SPECT system. The actual loading amount of aminopropyl groups was found about 1.6mmol per gram of final silica. The specific activity of the final compound was found to be 3Ci/g. Amine functionalized MCM-41 was found to be a good platform for theranostic radiopharmaceuticals such as copper-64 complexes. Considering the accumulation of the tracer in tumor cells, fast wash-out from normal tissues, the short half-life copper-64 and less imposed radiation doses to patients, [(64)Cu]-TPPF20@NH2-MCM-41 can potentially be a suitable candidate for tumor imaging applications and future PET studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Responses of hybrid striped bass to waterborne and dietary copper in freshwater and saltwater

USGS Publications Warehouse

Bielmyer, G.K.; Gatlin, D.; Isely, J.J.; Tomasso, J.; Klaine, S.J.

2005-01-01

Mechanisms of copper toxicity and consequences of exposure vary due to uptake route and ionoregulatory status. The goal of this research was to develop a model fish system to assess the influence of different Cu exposure routes (waterborne or dietary) on bioavailability, uptake, and effects in hybrid striped bass (Morone chrysops×Morone saxatilis) acclimated to fresh- or saltwater. Initially, hybrid striped bass were exposed to dietary Cu concentrations of 571, 785, and 1013 μg Cu/g, along with a control (∼ 5 μg Cu/g), for 14 days in saltwater. Intestinal and liver Cu accumulated in a dose-dependent manner in fish exposed to increasing levels of dietary Cu. Chronic (42 days) experiments were then conducted to determine sub-lethal effects of aqueous, dietary, and combined aqueous and dietary Cu exposures to both freshwater- and saltwater-acclimated hybrid striped bass. Growth and Cu accumulation in the gill, intestine, and liver were measured. Although no significant effects were observed in fish exposed to waterborne Cu, those exposed through the diet accumulated significant liver and intestinal Cu but showed no significant change in growth. Overall, these results suggest that at the levels tested, exposure to elevated waterborne Cu did not cause significant long-term tissue Cu accumulation, whereas dietary Cu exposure caused significant liver and intestinal Cu accumulation in hybrid striped bass which was comparable in both freshwater and saltwater (15 g/L).

Efficient removal of methyl orange using Cu2O as a dual function catalyst

NASA Astrophysics Data System (ADS)

Zhang, Fan; Dong, Guohui; Wang, Mian; Zeng, Yubin; Wang, Chuanyi

2018-06-01

In this study, we synthesized Cu2O particles with rough surfaces by a facile solvothermal method as a dual-function material that can degrade contaminants not only under light irradiation but also in dark circumstance. Both the as-prepared Cu2O and commercial Cu2O exhibited excellent performance for the removal of methyl orange under visible light irradiation through a photocatalysis-based strategy. However, the former was found to show remarkable capability under dark circumstances by means of molecular oxygen activation, while the latter performed poor efficiently under the same condition. This significant difference of performances under dark circumstances was related to rich oxygen vacancies existed on the as-prepared Cu2O surfaces that are associated with the single-electron reduction of O2 to generate radO2-, which play a dominant role in the generation of Cu+. In addition, Cu+ was identified to play key roles in the broken of azo bond. Then, the generated intermediates were mineralized by radOH generated through molecular oxygen activation process. This study could not only deep the understanding of the MO removal mechanism by Cu2O but also show a novel direction of amphibious application for photocatalytic materials.

Chamomile flower extract-directed CuO nanoparticle formation for its antioxidant and DNA cleavage properties.

PubMed

Duman, Fatih; Ocsoy, Ismail; Kup, Fatma Ozturk

2016-03-01

In this study, we report the synthesis of copper oxide nanoparticles (CuO NPs) using a medicinal plant (Matricaria chamomilla) flower extract as both reducing and capping agent and investigate their antioxidant activity and interaction with plasmid DNA (pBR322).The CuO NPs were characterized using Uv-Vis spectroscopy, FT-IR (Fourier transform infrared spectroscopy), DLS (dynamic light scattering), XRD (X-ray diffraction), EDX (energy-dispersive X-ray) spectroscopy and SEM (scanning electron microscopy). The CuO NPs exhibited nearly mono-distributed and spherical shapes with diameters of 140 nm size. UV-Vis absorption spectrum of CuO NPs gave a broad peak around 285 and 320 nm. The existence of functional groups on the surface of CuO NPs was characterized with FT-IR analysis. XRD pattern showed that the NPs are in the form of a face-centered cubic crystal. Zeta potential value was measured as -20 mV due to the presence of negatively charged functional groups in plant extract. Additionally, we demonstrated concentration-dependent antioxidant activity of CuO NPs and their interaction with plasmid DNA. We assumed that the CuO NPs both cleave and break DNA double helix structure. Copyright © 2015 Elsevier B.V. All rights reserved.

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

NASA Astrophysics Data System (ADS)

Moon, Ellen M.; Peacock, Caroline L.

2011-11-01

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

Remediation of sediment and water contaminated by copper in small-scaled constructed wetlands: effect of bioaugmentation and phytoextraction.

PubMed

Huguenot, D; Bois, P; Cornu, J Y; Jezequel, K; Lollier, M; Lebeau, T

2015-01-01

The use of plants and microorganisms to mitigate sediment contaminated by copper was studied in microcosms that mimic the functioning of a stormwater basin (SWB) connected to vineyard watershed. The impact of phytoremediation and bioaugmentation with siderophore-producing bacteria on the fate of Cu was studied in two contrasted (batch vs. semi-continuous) hydraulic regimes. The fate of copper was characterised following its discharge at the outlet of the microcosms, its pore water concentration in the sediment, the assessment of its bioaccessible fraction in the rhizosphere and the measurement of its content in plant tissues. Physico-chemical (pH, redox potential) and biological parameters (total heterotrophic bacteria) were also monitored. As expected, the results showed a clear impact of the hydraulic regime on the redox potential and thus on the pore water concentration of Cu. Copper in pore water was also dependent on the frequency of Cu-polluted water discharges. Repeated bioaugmentation increased the total heterotrophic microflora as well as the Cu bioaccessibility in the rhizosphere and increased the amount of Cu extracted by Phragmites australis by a factor of ~2. Sugar beet pulp, used as a filter to avoid copper flushing, retained 20% of outcoming Cu and led to an overall retention of Cu higher than 94% when arranged at the outlet of microcosms. Bioaugmentation clearly improved the phytoextraction rate of Cu in a small-scaled SWB designed to mimic the functioning of a full-size SWB connected to vineyard watershed. Highlights: Cu phytoextraction in constructed wetlands much depends on the hydraulic regime and on the frequency of Cu-polluted water discharges. Cu phytoextraction increases with time and plant density. Cu bioaccessibility can be increased by bioaugmentation with siderophore-producing bacteria.

Macroscopic and Molecular Investigations of Copper Sorption by a Steam-Activated Biochar

EPA Science Inventory

Excessive Cu concentration in water systems can negatively impact biological systems. Because Cu can form strong associations with organic functional groups, we examined the ability of biochar (an O-C-enriched organic bioenergy by-product) to sorb Cu frmo solution. In a batch e...

The effect of Mn/Ni on thermodynamic properties of critical nucleus in Fe-Cu-Mn (Ni) ternary alloys

DOE PAGES

Li, Boyan; Zhang, Lei; Li, Chengliang; ...

2018-04-18

The aging- or radiation-induced hardening of Cu/Mn/Ni precipitates in Fe alloys is one of property degradation mechanisms in structural materials in nuclear reactors. Experiments show that aging or radiation leads the formation of Cu-rich precipitates, and the addition of Mn or Ni elements enhances the precipitation kinetics. In this study, the phase-field model coupled with the constrained string method have been applied to investigate the thermodynamic properties of critical nuclei such as the minimum energy path of Cu/Mn/Ni precipitation in Fe-Cu-Mn and Fe-Cu-Ni ternary alloys. The chemical free energies used in the model are taken from CALPHAD. The simulation resultsmore » show that the formation of Cu/Mn/Ni clusters needs to overcome an energy barrier, and the precipitate has a Core-Shell structure. The thermodynamic properties of the critical nucleus are influenced by temperature and Cu/Mn/Ni overall concentrations, which are in accordance with the simulation results as well as the experimental observations.« less

The effect of Mn/Ni on thermodynamic properties of critical nucleus in Fe-Cu-Mn (Ni) ternary alloys

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

Li, Boyan; Zhang, Lei; Li, Chengliang

The aging- or radiation-induced hardening of Cu/Mn/Ni precipitates in Fe alloys is one of property degradation mechanisms in structural materials in nuclear reactors. Experiments show that aging or radiation leads the formation of Cu-rich precipitates, and the addition of Mn or Ni elements enhances the precipitation kinetics. In this study, the phase-field model coupled with the constrained string method have been applied to investigate the thermodynamic properties of critical nuclei such as the minimum energy path of Cu/Mn/Ni precipitation in Fe-Cu-Mn and Fe-Cu-Ni ternary alloys. The chemical free energies used in the model are taken from CALPHAD. The simulation resultsmore » show that the formation of Cu/Mn/Ni clusters needs to overcome an energy barrier, and the precipitate has a Core-Shell structure. The thermodynamic properties of the critical nucleus are influenced by temperature and Cu/Mn/Ni overall concentrations, which are in accordance with the simulation results as well as the experimental observations.« less

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

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

Gao, Weidong; Cao, Di; Jin, Yunxue

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

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

DOE PAGES

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

2018-04-18

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

Influence of Lu2O3 on electrical and microstructural properties of CaCu3Ti4O12 ceramics

NASA Astrophysics Data System (ADS)

Xu, Dong; Wang, Biao; Lin, Yuanhua; Jiao, Lei; Yuan, Hongming; Zhao, Guoping; Cheng, Xiaonong

2012-07-01

In this work, the influence of Lu2O3 doped on the dielectric and electrical properties of CaCu3Ti4O12 was reported. Lu2O3-doped CCTO was prepared by a conventional solid state technique using CuO, TiO2, and CaCO3 as starting materials. The samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM); dielectric measurements were measured in the 102 Hz-107 Hz frequency range at room temperature; and the nonlinear behavior of all samples was measured. The doping of Lu2O3 resulted in an increase in the dielectric constant of CCTO, but decreased the stability of the frequency dependence. Increasing concentrations of Lu2O3 resulted in decreasing nonlinear coefficients.

Optical and electrical properties of Cu-based all oxide semi-transparent photodetector

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

Kim, Hong-Sik; Patel, Malkeshkumar; Yadav, Pankaj

2016-09-05

Zero-bias operating Cu oxide-based photodetector was achieved by using large-scale available sputtering method. Cu oxide (Cu{sub 2}O or CuO) was used as p-type transparent layer to form a heterojunction by contacting n-type ZnO layer. All metal-oxide materials were employed to realize transparent device at room temperature and showed a high transparency (>75% at 600 nm) with excellent photoresponses. The structural, morphological, optical, and electrical properties of Cu oxides of CuO and Cu{sub 2}O are evaluated in depth by UV-visible spectrometer, X-ray diffraction, scanning electron microscopy, atomic force microscopy, Kelvin probe force microscopy, and Hall measurements. We may suggest a route ofmore » high-functional Cu oxide-based photoelectric devices for the applications in flexible and transparent electronics.« less

Corrosion resistance evaluation of Pd-free Ag-Au-Pt-Cu dental alloys.

PubMed

Fujita, Takeshi; Shiraishi, Takanobu; Takuma, Yasuko; Hisatsune, Kunihiro

2011-01-01

The corrosion resistance of nine experimental Pd-free Ag-Au-Pt-Cu dental alloys in a 0.9% NaCl solution was investigated using cyclic voltammetry (CV), optical microscopy, and scanning electron microscopy (SEM). CV measurements revealed that the breakdown potential (E(bd)) and zero current potential (E(zc)) increased with increasing Au/(Au+Ag) atomic ratio. Thus, the Au/(Au+Ag) atomic ratio, but not the Cu content, influenced the corrosion resistance of Ag-Au-Pt-Cu alloys. After the forward scan of CV, both optical and scanning electron microscope images showed that in all the experimental alloys, the matrix phase was corroded but not the second phase. From corrosion resistance viewpoint, the Ag-Au-Pt-Cu alloys seemed to be suitable for clinical application.

Indium-free, highly transparent, flexible Cu2O/Cu/Cu2O mesh electrodes for flexible touch screen panels

PubMed Central

Kim, Dong-Ju; Kim, Hyo-Joong; Seo, Ki-Won; Kim, Ki-Hyun; Kim, Tae-Wong; Kim, Han-Ki

2015-01-01

We report on an indium-free and cost-effective Cu2O/Cu/Cu2O multilayer mesh electrode grown by room temperature roll-to-roll sputtering as a viable alternative to ITO electrodes for the cost-effective production of large-area flexible touch screen panels (TSPs). By using a low resistivity metallic Cu interlayer and a patterned mesh structure, we obtained Cu2O/Cu/Cu2O multilayer mesh electrodes with a low sheet resistance of 15.1 Ohm/square and high optical transmittance of 89% as well as good mechanical flexibility. Outer/inner bending test results showed that the Cu2O/Cu/Cu2O mesh electrode had a mechanical flexibility superior to that of conventional ITO films. Using the diamond-patterned Cu2O/Cu/Cu2O multilayer mesh electrodes, we successfully demonstrated TSPS of the flexible film-film type and rigid glass-film-film type TSPs. The TSPs with Cu2O/Cu/Cu2O mesh electrode were used to perform zoom in/out functions and multi-touch writing, indicating that these electrodes are promising cost-efficient transparent electrodes to substitute for conventional ITO electrodes in large-area flexible TSPs. PMID:26582471

Indium-free, highly transparent, flexible Cu2O/Cu/Cu2O mesh electrodes for flexible touch screen panels.

PubMed

Kim, Dong-Ju; Kim, Hyo-Joong; Seo, Ki-Won; Kim, Ki-Hyun; Kim, Tae-Wong; Kim, Han-Ki

2015-11-19

We report on an indium-free and cost-effective Cu2O/Cu/Cu2O multilayer mesh electrode grown by room temperature roll-to-roll sputtering as a viable alternative to ITO electrodes for the cost-effective production of large-area flexible touch screen panels (TSPs). By using a low resistivity metallic Cu interlayer and a patterned mesh structure, we obtained Cu2O/Cu/Cu2O multilayer mesh electrodes with a low sheet resistance of 15.1 Ohm/square and high optical transmittance of 89% as well as good mechanical flexibility. Outer/inner bending test results showed that the Cu2O/Cu/Cu2O mesh electrode had a mechanical flexibility superior to that of conventional ITO films. Using the diamond-patterned Cu2O/Cu/Cu2O multilayer mesh electrodes, we successfully demonstrated TSPS of the flexible film-film type and rigid glass-film-film type TSPs. The TSPs with Cu2O/Cu/Cu2O mesh electrode were used to perform zoom in/out functions and multi-touch writing, indicating that these electrodes are promising cost-efficient transparent electrodes to substitute for conventional ITO electrodes in large-area flexible TSPs.

Indium-free, highly transparent, flexible Cu2O/Cu/Cu2O mesh electrodes for flexible touch screen panels

NASA Astrophysics Data System (ADS)

Kim, Dong-Ju; Kim, Hyo-Joong; Seo, Ki-Won; Kim, Ki-Hyun; Kim, Tae-Wong; Kim, Han-Ki

2015-11-01

We report on an indium-free and cost-effective Cu2O/Cu/Cu2O multilayer mesh electrode grown by room temperature roll-to-roll sputtering as a viable alternative to ITO electrodes for the cost-effective production of large-area flexible touch screen panels (TSPs). By using a low resistivity metallic Cu interlayer and a patterned mesh structure, we obtained Cu2O/Cu/Cu2O multilayer mesh electrodes with a low sheet resistance of 15.1 Ohm/square and high optical transmittance of 89% as well as good mechanical flexibility. Outer/inner bending test results showed that the Cu2O/Cu/Cu2O mesh electrode had a mechanical flexibility superior to that of conventional ITO films. Using the diamond-patterned Cu2O/Cu/Cu2O multilayer mesh electrodes, we successfully demonstrated TSPS of the flexible film-film type and rigid glass-film-film type TSPs. The TSPs with Cu2O/Cu/Cu2O mesh electrode were used to perform zoom in/out functions and multi-touch writing, indicating that these electrodes are promising cost-efficient transparent electrodes to substitute for conventional ITO electrodes in large-area flexible TSPs.

Cu-releasing bioactive glass/polycaprolactone coating on Mg with antibacterial and anticorrosive properties for bone tissue engineering.

PubMed

Yang, Yuyun; Zheng, Kai; Liang, Ruifang; Mainka, Astrid; Taccardi, Nicola; Roether, Judith A; Detsch, Rainer; Goldmann, Wolfgang H; Virtanen, Sannakaisa; Boccaccini, Aldo R

2017-10-26

Bioactive glass nanoparticles containing copper (Cu-BGNs) were introduced into polycaprolactone (PCL) coating systems to improve the bioactivity, antibacterial properties, and corrosion resistance of vulnerable magnesium matrices under physiological conditions. The influence of different amounts of Cu-BGNs in PCL coatings was thoroughly investigated in determining the wettability, electrochemical properties, and antibacterial effects against Staphylococcus carnosus and Escherichia coli, as well as their cyto-compatibility. Cu-BGNs were observed randomly scattered in PCL coatings. Increasing the concentration of Cu-BGNs resulted in a slight decrease of the water contact angle, and a reduction in anticorrosion properties of the Cu-BGN composite coatings. Yet higher Cu-BGN content in coatings led to more calcium phosphate formation on the surface after 7 days of immersion in Dulbecco's modified Eagle's medium, which was confirmed by Fourier-transform infrared spectroscopy and x-ray photoelectron spectroscopy. The growth of S. carnosus and E. coli was inhibited by Cu 2+ ions released from the Cu-BGN coatings. In addition, both direct and indirect cyto-compatibility experiments showed that the viability and proliferation of MG-63 cells on Cu-BGN coatings were highly increased compared to pure magnesium; however, an additional increase of Cu-BGN concentration showed a slight decrease of cell proliferation and cell activity. In summary, Cu-BGN/PCL composite coatings impart magnesium-based biomaterials with antibacterial and anticorrosive properties for clinical applications.

Abundant defects and defect clusters in kesterite Cu2ZnSnS4 and Cu2ZnSnSe4

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

Transformation of CuO Nanoparticles in the Aquatic Environment: Influence of pH, Electrolytes and Natural Organic Matter

PubMed Central

Peng, Cheng; Shen, Chensi; Zheng, Siyuan; Yang, Weiling; Hu, Hang; Liu, Jianshe; Shi, Jiyan

2017-01-01

Many studies have shown the effect of solution chemistry on the environmental behavior of metal-based nanoparticles (NPs), except CuO NPs. Here, we investigated the agglomeration, sedimentation, dissolution, and speciation of CuO NPs by varying pH, ionic strength, ionic valence, and natural organic matter (NOM). The results showed that as the pH moved away from 6, the size of CuO agglomerates decreased, along with the enhanced NP suspension stabilization, due to the increase of electrostatic repulsive force. Increasing ionic strength and valence intensified the agglomeration and sedimentation of CuO NPs because of the compression of electrical double layers. The presence of humic acid and citric acid enhanced the dispersion and stabilization of CuO NP suspension, but l-cysteine showed a different impact. Decreasing pH, increasing ionic strength and all NOM improved the dissolution of CuO NPs, but the divalent electrolyte (CaCl2) inhibited the Cu2+ release from CuO NPs compared to the monovalent electrolyte (NaCl). In addition, X-ray absorption near edge structure (XANES) analysis demonstrated that the presence of l-cysteine transformed more than 30% of CuO NPs to Cu(I)-cysteine by coordinating with thiol group. This study can give us an in-depth understanding on the environmental behavior and fate of CuO NPs in the aquatic environment. PMID:29036921

Mechanism and the origins of stereospecificity in copper-catalyzed ring expansion of vinyl oxiranes: a traceless dual transition-metal-mediated process.

PubMed

Mustard, Thomas J L; Mack, Daniel J; Njardarson, Jon T; Cheong, Paul Ha-Yeon

2013-01-30

Density functional theory computations of the Cu-catalyzed ring expansion of vinyloxiranes is mediated by a traceless dual Cu(I)-catalyst mechanism. Overall, the reaction involves a monomeric Cu(I)-catalyst, but a single key step, the Cu migration, requires two Cu(I)-catalysts for the transformation. This dual-Cu step is found to be a true double Cu(I) transition state rather than a single Cu(I) transition state in the presence of an adventitious, spectator Cu(I). Both Cu(I) catalysts are involved in the bond forming and breaking process. The single Cu(I) transition state is not a stationary point on the potential energy surface. Interestingly, the reductive elimination is rate-determining for the major diastereomeric product, while the Cu(I) migration step is rate-determining for the minor. Thus, while the reaction requires dual Cu(I) activation to proceed, kinetically, the presence of the dual-Cu(I) step is untraceable. The diastereospecificity of this reaction is controlled by the Cu migration step. Suprafacial migration is favored over antarafacial migration due to the distorted Cu π-allyl in the latter.

Influences of alkaline earth metal substitution on the crystal structure and physical properties of magnetic RuSr1.9A0.1GdCu2O8 (A = Ca, Sr, and Ba) superconductors.

PubMed

Hur, Su Gil; Park, Dae Hoon; Hwang, Seong-Ju; Kim, Seung Joo; Lee, J H; Lee, Sang Young

2005-11-24

We have investigated the effect of alkaline earth metal substitution on the crystal structure and physical properties of magnetic superconductors RuSr(1.9)A(0.1)GdCu(2)O(8) (A = Ca, Sr, and Ba) in order to probe an interaction between the magnetic coupling of the RuO(2) layer and the superconductivity of the CuO(2) layer. X-ray diffraction and X-ray absorption spectroscopic analyses demonstrate that the isovalent substitution of Sr ions with Ca or Ba ions makes it possible to tune the interlayer distance between the CuO(2) and the RuO(2) layers. From the measurements of electrical resistance and magnetic susceptibility, it was found that, in contrast to negligible change of magnetization, both of the alkaline earth metal substitutions lead to a notable depression of zero-resistance temperature T(c) (DeltaT(c) approximately 17-19 K). On the basis of the absence of a systematic correlation between the T(c) and the interlayer distance/magnetization, we have concluded that the internal magnetic field of the RuO(2) layer has insignificant influence on the superconducting property of the CuO(2) layer in the ruthenocuprate.

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

PubMed Central

Su, Ting; Zhang, Haifeng

2017-01-01

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

CuO-Functionalized Silicon Photoanodes for Photoelectrochemical Water Splitting Devices.

PubMed

Shi, Yuanyuan; Gimbert-Suriñach, Carolina; Han, Tingting; Berardi, Serena; Lanza, Mario; Llobet, Antoni

2016-01-13

One main difficulty for the technological development of photoelectrochemical (PEC) water splitting (WS) devices is the fabrication of active, stable and cost-effective photoelectrodes that ensure high performance. Here, we report the development of a CuO/Silicon based photoanode, which shows an onset potential for the water oxidation of 0.53 V vs SCE at pH 9, that is, an overpotential of 75 mV, and high stability above 10 h. These values account for a photovoltage of 420 mV due to the absorbed photons by silicon, as proven by comparing with analogous CuO/FTO electrodes that are not photoactive. The photoanodes have been fabricated by sputtering a thin film of Cu(0) on commercially available n-type Si wafers, followed by a photoelectrochemical treatment in basic pH conditions. The resulting CuO/Cu layer acts as (1) protective layer to avoid the corrosion of nSi, (2) p-type hole conducting layer for efficient charge separation and transportation, and (3) electrocatalyst to reduce the overpotential of the water oxidation reaction. The low cost, low toxicity, and good performance of CuO-based coatings can be an attractive solution to functionalize unstable materials for solar energy conversion.

Parasitization by Scleroderma guani influences expression of superoxide dismutase genes in Tenebrio molitor

USDA-ARS?s Scientific Manuscript database

Superoxide dismutase (SOD) is an antioxidant enzyme involved in detoxifying reactive oxygen species. In this study, we identified genes encoding the extracellular and intracellular copper-zinc SODs (ecCuZnSOD and icCuZnSOD) and a manganese SOD (MnSOD) in the yellow mealworm beetle, Tenebrio molitor....

Heteroepitaxial Cu 2O thin film solar cell on metallic substrates

DOE PAGES

Wee, Sung Hun; Huang, Po-Shun; Lee, Jung-Kun; ...

2015-11-06

Heteroepitaxial, single-crystal-like Cu 2O films on inexpensive, flexible, metallic substrates can potentially be used as absorber layers for fabrication of low-cost, high-performance, non-toxic, earth-abundant solar cells. Here, we report epitaxial growth of Cu 2O films on low cost, flexible, textured metallic substrates. Cu 2O films were deposited on the metallic templates via pulsed laser deposition under various processing conditions to study the influence of processing parameters on the structural and electronic properties of the films. It is found that pure, epitaxial Cu 2O phase without any trace of CuO phase is only formed in a limited deposition window of P(Omore » 2) - temperature. The (00l) single-oriented, highly textured, Cu 2O films deposited under optimum P(O 2) - temperature conditions exhibit excellent electronic properties with carrier mobility in the range of 40-60 cm 2 V -1 s -1 and carrier concentration over 10 16 cm -3. The power conversion efficiency of 1.65% is demonstrated from a proof-of-concept Cu 2O solar cell based on epitaxial Cu 2O film prepared on the textured metal substrate.« less

Adaptation of Selenastrum capricornutum (Chlorophyceae) to copper

USGS Publications Warehouse

Kuwabara, J.S.; Leland, H.V.

1986-01-01

Selenastrum capricornutum Printz, growing in a chemically defined medium, was used as a model for studying adaptation of algae to a toxic metal (copper) ion. Cells exhibited lag-phase adaptation to 0.8 ??M total Cu (10-12 M free ion concentration) after 20 generations of Cu exposure. Selenastrum adapted to the same concentration when Cu was gradually introduced over an 8-h period using a specially designed apparatus that provided a transient increase in exposure concentration. Cu adaptation was not attributable to media conditioning by algal exudates. Duration of lag phase was a more sensitive index of copper toxicity to Selenastrum that was growth rate or stationary-phase cell density under the experimental conditions used. Chemical speciation of the Cu dosing solution influenced the duration of lag phase even when media formulations were identical after dosing. Selenastrum initially exposed to Cu in a CuCl2 injection solution exhibited a lag phase of 3.9 d, but this was reduced to 1.5 d when a CuEDTA solution was used to achieve the same total Cu and EDTA concentrations. Physical and chemical processes that accelerated the rate of increase in cupric ion concentration generally increased the duration of lag phase. ?? 1986.

Heteroepitaxial Cu2O thin film solar cell on metallic substrates

PubMed Central

Wee, Sung Hun; Huang, Po-Shun; Lee, Jung-Kun; Goyal, Amit

2015-01-01

Heteroepitaxial, single-crystal-like Cu2O films on inexpensive, flexible, metallic substrates can potentially be used as absorber layers for fabrication of low-cost, high-performance, non-toxic, earth-abundant solar cells. Here, we report epitaxial growth of Cu2O films on low cost, flexible, textured metallic substrates. Cu2O films were deposited on the metallic templates via pulsed laser deposition under various processing conditions to study the influence of processing parameters on the structural and electronic properties of the films. It is found that pure, epitaxial Cu2O phase without any trace of CuO phase is only formed in a limited deposition window of P(O2) - temperature. The (00l) single-oriented, highly textured, Cu2O films deposited under optimum P(O2) - temperature conditions exhibit excellent electronic properties with carrier mobility in the range of 40–60 cm2 V−1 s−1 and carrier concentration over 1016 cm−3. The power conversion efficiency of 1.65% is demonstrated from a proof-of-concept Cu2O solar cell based on epitaxial Cu2O film prepared on the textured metal substrate. PMID:26541499

Electromigration in epitaxial Cu(001) lines

NASA Astrophysics Data System (ADS)

Ramanath, G.; Kim, H.; Goindi, H. S.; Frederick, M. J.; Shin, C.-S.; Goswami, R.; Petrov, I.; Greene, J. E.

2002-04-01

We report the electromigration (EM) response of single-domain epitaxial Cu(001) lines on layers of Ta, TaN, and TiN. Epitaxial Cu(001) lines on nitride layers exhibit nearly two orders of magnitude higher mean-time-to-failure (MTTF) values than those on Ta, indicating the strong influence of the underlayer. The activation energy of EM for Cu on the nitrides is ˜0.8-1.2 eV, and that of Cu on Ta is ˜0.2 eV, for 200-300 °C. Our results also indicate that the MTTF values correlate inversely to the crystal quality of the Cu layers measured by X-ray diffraction. The EM resistance of epitaxial Cu lines with different crystal quality on TaN were measured to separate the effects of interface chemistry and crystal quality. While higher quality epitaxial films reveal a higher EM resistance, the magnitude of the change is smaller than that obtained by changing the interface chemistry. Epitaxial lines exhibit more than 3-4 orders of magnitude higher MTTF than polycrystalline lines on the same underlayer. Based upon our results, we propose that the Cu/underlayer interface chemistry and presence of grain boundary diffusion play important roles in unpassivated Cu films.

Production and Isomeric Distribution of Xanthylium Cation Pigments and Their Precursors in Wine-like Conditions: Impact of Cu(II), Fe(II), Fe(III), Mn(II), Zn(II), and Al(III).

PubMed

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

2017-03-22

This study establishes the influence of Cu(II), Fe(II), Fe(III), Zn(II), Al(III), and Mn(II) on the oxidative production of xanthylium cations from (+)-catechin and either tartaric acid or glyoxylic acid in model wine systems. The reaction was studied at 25 °C using UHPLC and LC-HRMS for the analysis of phenolic products and their isomeric distribution. In addition to the expected products, a colorless product, tentatively assigned as a lactone, was detected for the first time. The results show the importance of Fe ions and a synergistic influence of Mn(II) in degrading tartaric acid to glyoxylic acid, whereas the other metal ions had minimal activity in this mechanistic step. Fe(II) and Fe(III) were shown to mediate the (+)-catechin-glyoxylic acid addition reaction, a role previously attributed to only Cu(II). Importantly, the study demonstrates that C-8 addition products of (+)-catechin are promoted by Cu(II), whereas C-6 addition products are promoted by Fe ions.

Nature of potential barrier in (Ca 1/4,Cu 3/4)TiO 3 polycrystalline perovskite

NASA Astrophysics Data System (ADS)

Marques, V. P. B.; Bueno, P. R.; Simões, A. Z.; Cilense, M.; Varela, J. A.; Longo, E.; Leite, E. R.

2006-04-01

The nonohmic electrical features of (Ca 1/4,Cu 3/4)TiO 3 perovskite ceramics, which have very strong gigantic dielectric is believed originate from potential barriers at the grain boundaries. In the present study, we used the admittance and impedance spectroscopy technique to investigate (Ca 1/4,Cu 3/4)TiO 3 perovskite ceramics with low nonohmic electrical properties. The study was conducted under two different conditions: on as-sintered ceramics and on ceramics thermally treated in an oxygen-rich atmosphere. The results confirm that thermal treatment in oxygen-rich atmospheres influence the nonohmic properties. Annealing at oxygen-rich atmospheres improve the nonohmic behavior and annealing at oxygen-poor atmospheres decrease the nonohmic properties, a behavior already reported for common metal oxide nonohmic devices and here firstly evidenced for the (Ca 1/4,Cu 3/4)TiO 3 perovskite related materials. The results show that oxygen also influences the capacitance values at low frequencies, a behavior that is indicative of the Schottky-type nature of the potential barrier.

Copper interstitial recombination centers in Cu3N

NASA Astrophysics Data System (ADS)

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; Hanifi, David; Salleo, Alberto; Magyari-Köpe, Blanka; Nishi, Yoshio; Bent, Stacey F.; Clemens, Bruce M.

2018-06-01

We present a comprehensive study of the earth-abundant semiconductor Cu3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies VCu have shallow defect levels while copper interstitials Cui behave as deep potential wells in the conduction band, which mediate Shockley-Read-Hall recombination. The existence of Cui defects has been experimentally verified using photothermal deflection spectroscopy. A Cu3N /ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. The absence of photocurrent can be explained by a large concentration of Cui recombination centers capturing electrons in p -type Cu3N .

Electrical Transport Properties of Liquid Al-Cu Alloys

NASA Astrophysics Data System (ADS)

Thakore, B. Y.; Khambholja, S. G.; Suthar, P. H.; Jani, A. R.

2010-06-01

Electrical transport properties viz. electrical resistivity, thermoelectric power and thermal conductivity of liquid Al-Cu alloys as a function of Cu concentration have been studied in the present paper. Ashcroft empty core model potential has been used to incorporate the ion-electron interaction. To incorporate the exchange and correlation effects, five different forms of local field correction functions viz. Hartree, Taylor, Ichimaru et al., Farid et al. and Sarkar et al. have been used. The transport properties of binary system have been studied using Faber-Ziman formulation combined with Ashcroft-Langreth (AL) partial structure factor. The computed values of electrical resistivity are compared with experimental data and for low Cu concentration, good agreement has been observed. Further, thermoelectric power and thermal conductivity have also been predicted.

Measurement of excitation functions in alpha induced reactions on natCu

NASA Astrophysics Data System (ADS)

Shahid, Muhammad; Kim, Kwangsoo; Kim, Guinyun; Zaman, Muhammad; Nadeem, Muhammad

2015-09-01

The excitation functions of 66,67,68Ga, 62,63,65Zn, 61,64Cu, and 58,60Co radionuclides in the natCu(α, x) reaction were measured in the energy range from 15 to 42 MeV by using a stacked-foil activation method at the MC-50 cyclotron of the Korean Institute of Radiological and Medical Sciences. The measured results were compared with the literature data as well as the theoretical values obtained from the TENDL-2013 and TENDL-2014 libraries based on the TALYS-1.6 code. The integral yields for thick targets of the produced radionuclides were also determined from the measured excitation functions and the stopping power of natural copper.

Towards Binding Mechanism of Cu2+ on Creatine Kinase from Pelodiscus sinensis: Molecular Dynamics Simulation Integrating Inhibition Kinetics Study.

PubMed

Cai, Yan; Lee, Jinhyuk; Wang, Wei; Park, Yong-Doo; Qian, Guo-Ying

2017-01-01

Cu2+ is well known to play important roles in living organisms having bifacial distinction: essential microelement that is necessary for a wide range of metabolic processes but hyper-accumulation of Cu2+ can be toxic. The physiological function of Cu2+ in ectothermic animals such as Pelodiscus sinensis (Chinese soft-shelled turtle) has not been elucidated. In this study, we elucidated effect of Cu2+ on the energy producing metabolic enzyme creatine kinase (CK), which might directly affect energy metabolism and homeostasis of P. sinensis. We first conducted molecular dynamics (MD) simulations between P-CK and Cu2+ and conducted the inactivation kinetics including spectrofluorimetry study. MD simulation showed that Cu2+ blocked the binding site of the ATP cofactor, indicating that Cu2+ could directly inactivate P-CK. We prepared the muscle type of CK (P-CK) and confirmed that Cu2+ conspicuously inactivated the activity of P-CK (IC50 = 24.3 μM) and exhibited non-competitive inhibition manner with creatine and ATP in a first-order kinetic process. This result was well matched to the MD simulation results that Cu2+-induced non-competitive inactivation of P-CK. The spectrofluorimetry study revealed that Cu2+ induced tertiary structure changes in PCK accompanying with the exposure of hydrophobic surfaces. Interestingly, the addition of osmolytes (glycine, proline, and liquaemin) effectively restored activity of the Cu2+-inactivated P-CK. Our study illustrates the Cu2+-mediated unfolding of P-CK with disruption of the enzymatic function and the protective restoration role of osmolytes on P-CK inactivation. This study provides information of interest on P-CK as a metabolic enzyme of ectothermic animal in response to Cu2+ binding. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Transcriptional and functional studies of Acidithiobacillus ferrooxidans genes related to survival in the presence of copper.

PubMed

Navarro, Claudio A; Orellana, Luis H; Mauriaca, Cecilia; Jerez, Carlos A

2009-10-01

The acidophilic Acidithiobacillus ferrooxidans can resist exceptionally high copper (Cu) concentrations. This property is important for its use in biomining processes, where Cu and other metal levels range usually between 15 and 100 mM. To learn about the mechanisms that allow A. ferrooxidans cells to survive in this environment, a bioinformatic search of its genome showed the presence of at least 10 genes that are possibly related to Cu homeostasis. Among them are three genes coding for putative ATPases related to the transport of Cu (A. ferrooxidans copA1 [copA1(Af)], copA2(Af), and copB(Af)), three genes related to a system of the resistance nodulation cell division family involved in the extraction of Cu from the cell (cusA(Af), cusB(Af), and cusC(Af)), and two genes coding for periplasmic chaperones for this metal (cusF(Af) and copC(Af)). The expression of most of these open reading frames was studied by real-time reverse transcriptase PCR using A. ferrooxidans cells adapted for growth in the presence of high concentrations of Cu. The putative A. ferrooxidans Cu resistance determinants were found to be upregulated when this bacterium was exposed to Cu in the range of 5 to 25 mM. These A. ferrooxidans genes conferred to Escherichia coli a greater Cu resistance than wild-type cells, supporting their functionality. The results reported here and previously published data strongly suggest that the high resistance of the extremophilic A. ferrooxidans to Cu may be due to part or all of the following key elements: (i) a wide repertoire of Cu resistance determinants, (ii) the duplication of some of these Cu resistance determinants, (iii) the existence of novel Cu chaperones, and (iv) a polyP-based Cu resistance system.

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

Srivastava, Himanshu; Ganguli, Tapas; Deb, S. K.

Growth of CuO nanowires by annealing method has been studied in-situ by grazing incidence Energy Dispersive X-ray Diffraction (EDXRD) technique on Indus-2. It was observed that Cu slowly oxidized to Cu{sub 2}O and finally to CuO. The data was taken as a function of time at two annealing temperatures 500 Degree-Sign C where nanowires form and 300 Degree-Sign C where nanowires don't form. We found that the strain in the CuO layer may be a principal factor for the spontaneous growth of nanowires in annealing method.

Methane monooxygenase gene expression mediated by methanobactin in the presence of mineral copper sources

PubMed Central

Knapp, Charles W.; Fowle, David A.; Kulczycki, Ezra; Roberts, Jennifer A.; Graham, David W.

2007-01-01

Methane is a major greenhouse gas linked to global warming; however, patterns of in situ methane oxidation by methane-oxidizing bacteria (methanotrophs), nature's main biological mechanism for methane suppression, are often inconsistent with laboratory predictions. For example, one would expect a strong relationship between methanotroph ecology and Cu level because methanotrophs require Cu to sustain particulate methane monooxygenase (pMMO), the most efficient enzyme for methane oxidation. However, no correlation has been observed in nature, which is surprising because methane monooxygenase (MMO) gene expression has been unequivocally linked to Cu availability. Here we provide a fundamental explanation for this lack of correlation. We propose that MMO expression in nature is largely controlled by solid-phase Cu geochemistry and the relative ability of Cu acquisition systems in methanotrophs, such as methanobactins (mb), to obtain Cu from mineral sources. To test this hypothesis, RT-PCR expression assays were developed for Methylosinus trichosporium OB3b (which produces mb) to quantify pMMO, soluble MMO (the alternate MMO expressed when Cu is “unavailable”), and 16S-rRNA gene expression under progressively more stringent Cu supply conditions. When Cu was provided as CuCl2, pMMO transcript levels increased significantly consistent with laboratory work. However, when Cu was provided as Cu-doped iron oxide, pMMO transcript levels increased only when mb was also present. Finally, when Cu was provided as Cu-doped borosilicate glass, pMMO transcription patterns varied depending on the ambient mb:Cu supply ratio. Cu geochemistry clearly influences MMO expression in terrestrial systems, and, as such, local Cu mineralogy might provide an explanation for methane oxidation patterns in the natural environment. PMID:17615240

High T c superconductivity in YBa2Cu3O7- x studied by PAC and PAS

NASA Astrophysics Data System (ADS)

Zhu, Shengyun; Li, Anli; Zheng, Shengnan; Huang, Hanchen; Li, Donghong; Din, Honglin; Du, Hongshan; Sun, Hancheng

1993-03-01

High T c superconductivity has been investigated in YBaCuO by both perturbed angular correlation and positron annihilation spectroscopy techniques as a function of temperature from 77 to 300 K. An abrupt change has been observed in the positron lifetime and Doppler broadening and the electric field gradient and its asymmetry parameter across T c, indicating a transition of two- to one-dimensional Cu-O-Cu chain structure and a charge transfer from CuO layers to CuO chains. An anomaly of the normal state has been demonstrated around 125 K, which is attributed to the structural instability.

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

PubMed

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

2017-08-02

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

Streptomyces communities in soils polluted with heavy metals

NASA Astrophysics Data System (ADS)

Grishko, V. N.; Syshchikova, O. V.

2009-02-01

The contents of differently mobile heavy metal compounds and their influence on the formation of microbial cenoses (particularly, streptomyces communities) in technogenically disturbed soils are considered. Elevated concentrations of mobile Cu, Zn, Ni, Cd, and Fe compounds are shown to determine structural-functional changes in microbial cenoses that are displayed in a decreasing number of microorganisms and a narrower spectrum of the streptomyces species. Some specific features of the formation of streptomyces communities in technogenic soils were revealed on the basis of the analysis of their species structure with the use of the Margalef, Berger-Parker, and Sorensen indices of biodiversity.

Measurement of regional cerebral blood flow with copper-62-PTSM and a three-compartment model.

PubMed

Okazawa, H; Yonekura, Y; Fujibayashi, Y; Mukai, T; Nishizawa, S; Magata, Y; Ishizu, K; Tamaki, N; Konishi, J

1996-07-01

We evaluated quantitatively 62Cu-labeled pyruvaldehyde bis(N4-methylthiosemicarbazone) copper II (62Cu-PTSM) as a brain perfusion tracer for positron emission tomography (PET). For quantitative measurement, the octanol extraction method is needed to correct for arterial radioactivity in estimating the lipophilic input function, but the procedure is not practical for clinical studies. To measure regional cerebral blood flow (rCBF) by 62Cu-PTSM with simple arterial blood sampling, a standard curve of the octanol extraction ratio and a three-compartment model were applied. We performed both 15O-labeled water PET and 62 Cu-PTSM PET with dynamic data acquisition and arterial sampling in six subjects. Data obtained in 10 subjects studied previously were used for the standard octanol extraction curve. Arterial activity was measured and corrected to obtain the true input function using the standard curve. Graphical analysis (Gjedde-Patlak plot) with the data for each subject fitted by a straight regression line suggested that 62Cu-PTSM can be analyzed by the three-compartment model with negligible K4. Using this model, K1-K3 were estimated from curve fitting of the cerebral time-activity curve and the corrected input function. The fractional uptake of 62Cu-PTSM was corrected to rCBF with the individual extraction at steady state calculated from K1-K3. The influx rates (Ki) obtained from three-compartment model and graphical analyses were compared for the validation of the model. A comparison of rCBF values obtained from 62Cu-PTSM and 150-water studies demonstrated excellent correlation. The results suggest the potential feasibility of quantitation of cerebral perfusion with 62Cu-PTSM accompanied by dynamic PET and simple arterial sampling.

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition

PubMed Central

Song, Han Byul; Wang, Xiance; Patton, James R.; Stansbury, Jeffrey W.; Bowman, Christopher N.

2017-01-01

Objectives Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Methods Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized silica microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. Results The photo-CuAAC polymerization of composites containing between 0 and 60 wt% microfiller achieved ~99% conversion with a dramatic reduction in the maximum heat of reaction (~20 °C decrease) for the 60 wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60 wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01 MPa, equivalent flexural modulus of 6.1±0.7 GPa, equivalent flexural strength of 107±9 MPa, and more than 10 times higher energy absorption of 10±1 MJ m−3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Significance Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. PMID:28363645

Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

PubMed

Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N

2017-06-01

Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm -3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A novel extended architecture with 4 6·6 4 topology based on mixed-valence Wells-Dawson arsenotungstate and mixed-ligand Cu(I) units

NASA Astrophysics Data System (ADS)

Tong, Ruizhan; Ren, Xiaoyu; Li, Zuoxi; Liu, Bin; Hu, Huaiming; Xue, Ganglin; Fu, Feng; Wang, Jiwu

2010-09-01

A novel inorganic-organic hybrid compound based on mixed-valence Wells-Dawson arsenotungstate and mixed-ligand Cu(I) units, Cu 8I(imi) 4(bpy) 6(H 2O)[As 2VW 2VW 16VlO 62]·2H 2O ( 1) (bpy=4,4'-bipydine; imi=imidazole), has been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, luminescent spectrum and single crystal X-ray diffraction. Single-crystal X-ray diffraction revealed that four terminal and three bridging oxygen atoms of the Wells-Dawson cluster are coordinated to Cu(I) ions and form an unprecedented hepta-supporting polyoxometalate. The functionalized arsenotungstates are further connected by two kinds of tridentate linkers, Imi-Cu-(bpy)-Cu-(bpy)-Cu-(bpy)-Cu-Imi and Imi-Cu-(bpy)-Cu-(bpy)-Cu-H 2O, to construct a 3D framework with 4 6·6 4 topology. The hybrid material has an intense emission at about 397 nm.

Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

DOE PAGES

Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

2016-02-23

Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111)more » through an η 2(C,O) configuration which led to the HDO of furfural on Ni/Cu(111). Lastly, the ability to dissociate H 2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).« less

Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

NASA Astrophysics Data System (ADS)

Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

2016-10-01

Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).

Effect of immersion time in a modified green death solution on the rust layer of Cu-containing low-alloy steel

NASA Astrophysics Data System (ADS)

Kim, Seon-Hong; Kwon, Min-Seok; Kim, Jung-Gu

2017-01-01

The corrosion resistance of low-alloy steel containing 0.35 wt% copper, as a function of immersion time in a modified green death solution, was investigated using electrochemical methods and surface analysis. After 30 min of immersion, the steel surface was covered with a Cu-enriched film. Improvement of the film properties and increases in the corrosion resistance were realized for the immersion time up to 6 h due to the development of the Cu-enriched layer. However, the Cu particle was formed in the Cu-enriched layer for the immersion time beyond 6 h. Since the formation of the Cu particle generated a Cu-depletion region, micro-galvanic corrosion between the Cu particle and the Cu-depletion region lead to the localized film breakdown on the surface film. The localized film breakdown, which decreased the corrosion properties of the Cu-containing steel, was accelerated by the continuous formation of Cu particles in the rust layer.

Influence of Cu Addition on the Structure, Mechanical and Corrosion Properties of Cast Mg-2%Zn Alloy

NASA Astrophysics Data System (ADS)

Lotfpour, M.; Emamy, M.; Dehghanian, C.; Tavighi, K.

2017-05-01

Effects of different concentrations of Cu on the structure, mechanical and corrosion properties of Mg-2%Zn alloy were studied by the use of x-ray diffraction, optical microscopy, scanning electron microscopy, energy dispersive spectroscopy, standard tensile testing, polarization and electrochemical impedance spectroscopy (EIS) measurements. The average grain size of the alloy decreased from above 1000 μm to about 200 μm with 5 wt.% Cu addition in as-cast condition. Microstructural studies revealed that Mg-2Zn- xCu alloys matrix typically consists of primary α-Mg and MgZnCu and Mg(Zn,Cu)2 intermetallics which are mainly found at the grain boundaries. The results obtained from mechanical testing ascertained that Cu addition increased the hardness values significantly. Although the addition of 0.5 wt.% Cu improved the ultimate tensile strength and elongation values, more Cu addition (i.e., 5 wt.%) weakened the tensile properties of the alloy by introducing semi-continuous network of brittle intermetallic phases. Based on polarization test results, it can be concluded that Cu eliminates a protective film on Mg-2%Zn alloy surface. Among Mg-2%Zn- x%Cu alloys, the one containing 0.1 wt.% Cu exhibited the best anti-corrosion property. However, further Cu addition increased the volume fraction of intermetallics culminating in corrosion rate enhancement due to the galvanic couple effect. EIS and microstructural analysis also confirmed the polarization results.

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

Development and Status of Cu Ball/Wedge Bonding in 2012

NASA Astrophysics Data System (ADS)

Schneider-Ramelow, Martin; Geißler, Ute; Schmitz, Stefan; Grübl, Wolfgang; Schuch, Bernhard

2013-03-01

Starting in the 1980s and continuing right into the last decade, a great deal of research has been published on Cu ball/wedge (Cu B/W) wire bonding. Despite this, the technology has not been established in industrial manufacturing to any meaningful extent. Only spikes in the price of Au, improvements in equipment and techniques, and better understanding of the Cu wire-bonding process have seen Cu B/W bonding become more widespread—initially primarily for consumer goods manufacturing. Cu wire bonding is now expected to soon be used for at least 20% of all ball/wedge-bonded components, and its utilization in more sophisticated applications is around the corner. In light of this progress, the present paper comprehensively reviews the existing literature on this topic and discusses wire-bonding materials, equipment, and tools in the ongoing development of Cu B/W bonding technology. Key bonding techniques, such as flame-off, how to prevent damage to the chip (cratering), and bond formation on various common chip and substrate finishes are also described. Furthermore, apart from discussing quality assessment of Cu wire bonds in the initial state, the paper also provides an overview of Cu bonding reliability, in particular regarding Cu balls on Al metalization at high temperatures and in humidity (including under the influence of halide ions).

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

Preparation of flower-like CuS by solvothermal method for photocatalytic, UV protection and EMI shielding applications

NASA Astrophysics Data System (ADS)

Hu, Xiao-Sai; Shen, Yong; Xu, Li-Hui; Wang, Li-Ming; Lu, Li-sha; Zhang, Ya-ting

2016-11-01

The flower-like CuS hierarchical structures were synthesized by solvothermal method. The as-prepared products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared(FTIR) spectroscopy, UV-vis optical absorption spectroscopy and thermogravimetric analysis (TGA). The results demonstrated that the as-prepared flower-like CuS with the diameter of 1-5 um was pure hexagonal phase CuS and had well-defined flower-like structures. (1) The as-prepared CuS was proved to possess high photocatalytic performance with band gap of 1.45 eV. The degradation rate of Methylene blue (MB) was up to, 98.26%, 100% after 30 min under UV and visible irradiation. (2)The UPF of cotton fabric treated with CuS reached up to 174 compared with the original untreated fabric with the UPF 20.62. (3) The electromagnetic interference shielding effectiveness (EMI SE) of CuS coating was up to 27-31 dB when the content of CuS increased to 28.6%wt in the frequency of 300 KHz-3 GHz. Furthermore, the influence of reaction conditions on the morphology of the as-prepared CuS was investigated systematically and the possible formation mechanism of the CuS hierarchical structure was also proposed.

Stable isotope tracing of Ni and Cu pollution in North-East Norway: Potentials and drawbacks.

PubMed

Šillerová, Hana; Chrastný, Vladislav; Vítková, Martina; Francová, Anna; Jehlička, Jan; Gutsch, Marissa R; Kocourková, Jana; Aspholm, Paul E; Nilsson, Lars O; Berglen, Tore F; Jensen, Henning K B; Komárek, Michael

2017-09-01

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM 10 ). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ 60 Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ 65 Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ 60 Ni and δ 65 Cu values determined in the smelter, i.e. in feeding material and slag (δ 60 Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ 65 Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ 60 Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ 65 Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of silicon on wheat seedlings (Triticum turgidum L.) grown in hydroponics and exposed to 0 to 30 µM Cu.

PubMed

Keller, C; Rizwan, M; Davidian, J-C; Pokrovsky, O S; Bovet, N; Chaurand, P; Meunier, J-D

2015-04-01

Aqueous Si limits Cu uptake by a Si-accumulating plant via physicochemical mechanisms occurring at the root level. Sufficient Si supply may alleviate Cu toxicity in Cu-contaminated soils. Little information is available on the role of silicon (Si) in copper (Cu) tolerance while Cu toxicity is widespread in crops grown on Cu-contaminated soils. A hydroponic study was set up to investigate the influence of Si on Cu tolerance in durum wheat (Triticum turgidum L.) grown in 0, 0.7, 7.0 and 30 µM Cu without and with 1.0 mM Si, and to identify the mechanisms involved in mitigation of Cu toxicity. Si supply alleviated Cu toxicity in durum wheat at 30 µM Cu, while Cu significantly increased Si concentration in roots. Root length, photosynthetic pigments concentrations, macroelements, and organic anions (malate, acetate and aconitate) in roots, were also increased. Desorption experiments, XPS analysis of the outer thin root surface (≤100 Å) and µXRF analyses showed that Si increased adsorption of Cu at the root surface as well as Cu accumulation in the epidermis while Cu was localised in the central cylinder when Si was not applied. Copper was not detected in phytoliths. This study provides evidences for Si-mediated alleviation of Cu toxicity in durum wheat. It also shows that Si supplementation to plants exposed to increasing levels of Cu in solution induces non-simultaneous changes in physiological parameters. We propose a three-step mechanism occurring mainly at the root level and limiting Cu uptake and translocation to shoots: (i) increased Cu adsorption onto the outer thin layer root surface and immobilisation in the vicinity of root epidermis, (ii) increased Cu complexation by both inorganic and organic anions such as aconitate and, (iii) limitation of translocation through an enhanced thickening of a Si-loaded endodermis.

[Use of dinoflagellates as a metal toxicity assessment tool in aquatic system].

PubMed

Yuan, Li-juan; He, Meng-chang

2009-10-15

Although dinoflagellates have been used to assess biological toxicity of contaminants, this method still lacks of corresponding toxicity assessment standard. This study appraised the toxicity of selected heavy metals to dinoflagellates based on the dinoflagellates bioluminescence with QwikLite developed by the United States Navy. The results show that single heavy metal biological toxicity is in the order: Hg2+ > Cu2+ > Cd2+ > As5+ > Pb2+ > Cr6+; Two, three and four heavy metal mixture experiments show synergism primarily, antagonism is in minority. pH has not remarkable effect on dinoflagellates, they can be applied directly in natural water, but pH influence Hg2+ and Cu2+ toxicity greatly, eliminating the influence of pH is essential when doing these two kind of ions measurements. The nutrients has little influence on dinoflagellates, change in COD has obvious effect on the response relationships between dinoflagellates and Hg2+ or CU2+. Metal toxicity assessment using dinoflagellates shows great sensitivity, narrow response scope and high stability. Dinoflagellates are good species for heavy metal biological toxicity test in aquatic system.

Influence of composition on the performance of sintered Cu(In,Ga)Se2 nanocrystal thin-film photovoltaic devices.

PubMed

Akhavan, Vahid A; Harvey, Taylor B; Stolle, C Jackson; Ostrowski, David P; Glaz, Micah S; Goodfellow, Brian W; Panthani, Matthew G; Reid, Dariya K; Vanden Bout, David A; Korgel, Brian A

2013-03-01

Thin-film photovoltaic devices (PVs) were prepared by selenization using oleylamine-capped Cu(In,Ga)Se2 (CIGS) nanocrystals sintered at a high temperature (>500 °C) under Se vapor. The device performance varied significantly with [Ga]/[In+Ga] content in the nanocrystals. The highest power conversion efficiency (PCE) observed in the devices studied was 5.1 % under air mass 1.5 global (AM 1.5 G) illumination, obtained with [Ga]/[In+Ga]=0.32. The variation in PCE with composition is partly a result of bandgap tuning and optimization, but the main influence of nanocrystal composition appeared to be on the quality of the sintered films. The [Cu]/[In+Ga] content was found to be strongly influenced by the [Ga]/[In+Ga] concentration, which appears to be correlated with the morphology of the sintered film. For this reason, only small changes in the [Ga]/[In+Ga] content resulted in significant variations in device efficiency. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Top-down and bottom-up attention-to-memory: mapping functional connectivity in two distinct networks that underlie cued and uncued recognition memory.

PubMed

Burianová, Hana; Ciaramelli, Elisa; Grady, Cheryl L; Moscovitch, Morris

2012-11-15

The objective of this study was to examine the functional connectivity of brain regions active during cued and uncued recognition memory to test the idea that distinct networks would underlie these memory processes, as predicted by the attention-to-memory (AtoM) hypothesis. The AtoM hypothesis suggests that dorsal parietal cortex (DPC) allocates effortful top-down attention to memory retrieval during cued retrieval, whereas ventral parietal cortex (VPC) mediates spontaneous bottom-up capture of attention by memory during uncued retrieval. To identify networks associated with these two processes, we conducted a functional connectivity analysis of a left DPC and a left VPC region, both identified by a previous analysis of task-related regional activations. We hypothesized that the two parietal regions would be functionally connected with distinct neural networks, reflecting their engagement in the differential mnemonic processes. We found two spatially dissociated networks that overlapped only in the precuneus. During cued trials, DPC was functionally connected with dorsal attention areas, including the superior parietal lobules, right precuneus, and premotor cortex, as well as relevant memory areas, such as the left hippocampus and the middle frontal gyri. During uncued trials, VPC was functionally connected with ventral attention areas, including the supramarginal gyrus, cuneus, and right fusiform gyrus, as well as the parahippocampal gyrus. In addition, activity in the DPC network was associated with faster response times for cued retrieval. This is the first study to show a dissociation of the functional connectivity of posterior parietal regions during episodic memory retrieval, characterized by a top-down AtoM network involving DPC and a bottom-up AtoM network involving VPC. Copyright © 2012 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Nishihara, Hironori; Maeda, Tsuyoshi; Wada, Takahiro

2018-02-01

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

Theoretical calculation of the melting curve of Cu-Zr binary alloys

DOE PAGES

Gunawardana, K. G.S.H.; Wilson, S. R.; Mendelev, M. I.; ...

2014-11-14

Helmholtz free energies of the dominant binary crystalline solids found in the Cu-Zr system at high temperatures close to the melting curve are calculated. This theoretical approach combines fundamental measure density functional theory (applied to the hard-sphere reference system) and a perturbative approach to include the attractive interactions. The studied crystalline solids are Cu(fcc), Cu 51Zr 14(β), CuZr(B 2), CuZr 2(C11b), Zr(hcp), and Zr(bcc). The calculated Helmholtz free energies of crystalline solids are in good agreement with results from molecular-dynamics (MD) simulations. Using the same perturbation approach, the liquid phase free energies are calculated as a function of composition andmore » temperature, from which the melting curve of the entire composition range of this system can be obtained. Phase diagrams are determined in this way for two leading embedded atom method potentials, and the results are compared with experimental data. Furthermore, theoretical melting temperatures are compared both with experimental values and with values obtained directly from MD simulations at several compositions.« less

Low nitric oxide: a key factor underlying copper-deficiency teratogenicity.

PubMed

Yang, Soo Jin; Keen, Carl L; Lanoue, Louise; Rucker, Robert B; Uriu-Adams, Janet Y

2007-12-15

Copper (Cu)-deficiency-induced teratogenicity is characterized by major cardiac, brain, and vascular anomalies; however, the underlying mechanisms are poorly understood. Cu deficiency decreases superoxide dismutase activity and increases superoxide anions, which can interact with nitric oxide (NO), reducing the NO pool size. Given the role of NO as a developmental signaling molecule, we tested the hypothesis that low NO levels, secondary to Cu deficiency, represent a developmental challenge. Gestation day 8.5 embryos from Cu-adequate (Cu+) or Cu-deficient (Cu-) dams were cultured for 48 h in Cu+ or Cu- medium, respectively. We report that NO levels were low in conditioned medium from Cu-/Cu- embryos and yolk sacs, compared to Cu+/Cu+ controls under basal conditions and with NO synthase (NOS) agonists. The low NO production was associated with low endothelial NOS phosphorylation at serine 1177 and cyclic guanosine-3',5'-monophosphate (cGMP) concentrations in the Cu-/Cu- group. The altered NO levels in Cu-deficient embryos are functionally significant, as the administration of the NO donor DETA/NONOate increased cGMP and ameliorated embryo and yolk sac abnormalities. These data support the concept that Cu deficiency limits NO availability and alters NO-dependent signaling, which contributes to abnormal embryo and yolk sac development.

Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying

NASA Astrophysics Data System (ADS)

Barman, Sajib K.; Huda, Muhammad N.

2018-04-01

As a potential solar absorber material, Cu2S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu2S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu2S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu2S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu2S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu2S, and proposed a possible route to stabilize Cu2S against Cu vacancy formations by alloying it with Ag.

Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying.

PubMed

Barman, Sajib K; Huda, Muhammad N

2018-04-25

As a potential solar absorber material, Cu 2 S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu 2 S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu 2 S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu 2 S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu 2 S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu 2 S, and proposed a possible route to stabilize Cu 2 S against Cu vacancy formations by alloying it with Ag.

Inhibition and oxygen activation in copper amine oxidases.

PubMed

Shepard, Eric M; Dooley, David M

2015-05-19

Copper-containing amine oxidases (CuAOs) use both copper and 2,4,5-trihydroxyphenylalanine quinone (TPQ) to catalyze the oxidative deamination of primary amines. The CuAO active site is highly conserved and comprised of TPQ and a mononuclear type II copper center that exhibits five-coordinate, distorted square pyramidal coordination geometry with histidine ligands and equatorially and axially bound water in the oxidized, resting state. The active site is buried within the protein, and CuAOs from various sources display remarkable diversity with respect to the composition of the active site channel and cofactor accessibility. Structural and mechanistic factors that influence substrate preference and inhibitor sensitivity and selectivity have been defined. This Account summarizes the strategies used to design selective CuAO inhibitors based on active site channel characteristics, leading to either enhanced steric fits or the trapping of reactive electrophilic products. These findings provide a framework to support the future development of candidate molecules aimed at minimizing the negative side effects associated with drugs containing amine functionalities. This is vital given the existence of human diamine oxidase and vascular adhesion protein-1, which have distinct amine substrate preferences and are associated with different metabolic processes. Inhibition of these enzymes by antifungal or antiprotozoal agents, as well as classic monoamine oxidase (MAO) inhibitors, may contribute to the adverse side effects associated with drug treatment. These observations provide a rationale for the limited clinical value associated with certain amine-containing pharmaceuticals and emphasize the need for more selective AO inhibitors. This Account also discusses the novel roles of copper and TPQ in the chemistry of O2 activation and substrate oxidation. Reduced CuAOs exist in a redox equilibrium between the Cu(II)-TPQAMQ (aminoquinol) and Cu(I)-TPQSQ (semiquinone). Elucidating the roles of Cu(I), TPQSQ, and TPQAMQ in O2 activation, for example, distinguishing inner-sphere versus outer-sphere electron transfer mechanisms, has been actively investigated since the discovery of TPQSQ in 1991 and has only recently been clarified. Kinetics and spectroscopic studies encompassing metal substitution, stopped-flow and temperature-jump relaxation methods, and oxygen kinetic isotope experiments have provided strong support for an inner-sphere electron transfer step from Cu(I) to O2. Data for two enzymes support a mechanism wherein O2 prebinds to a three-coordinate Cu(I) site, yielding a [Cu(II)(η(1)-O2(-1))](+) intermediate, with H2O2 generated from ensuing rate-determining proton coupled electron transfer from TPQSQ. While kinetics data from the cobalt-substituted yeast enzyme indicated that O2 is reduced through an outer-sphere process involving TPQAMQ, new findings with a bacterial CuAO demonstrate that both the Cu(II) and Co(II) forms of the enzyme operate via parallel mechanisms involving metal-superoxide intermediates. Structural observations of a coordinated TPQSQ-Cu(I) complex in two CuAOs supports previous indications that Cu(II)/(I) ligand substitution chemistry may be mechanistically relevant. Substantial evidence indicates that rapid and reversible inner-sphere reduction of O2 at a three-coordinate Cu(I) site occurs, but the existence of a coordinated semiquinone in some AOs suggests that, in these enzymes, an outer-sphere reaction between O2 and TPQSQ may also be possible, since this is expected to be energetically favorable compared with outer-sphere electron transfer from TPQAMQ to O2.

Electronic properties of the interface between hexadecafluoro copper phthalocyanine and unsubstituted copper phthalocyanine films

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

Komolov, A. S., E-mail: akomolov07@ya.ru; Lazneva, E. F.; Pshenichnyuk, S. A.

2013-07-15

The formation of an interface during the deposition of unsubstituted copper phthalocyanine (CuPc) films on the surface of hexadecafluoro copper phthalocyanine (F{sub 16}-CuPc) films is studied. An incident low-energy electron beam with energies from 0 to 25 eV is used to test the surface under study according to the very-low-energy electron-diffraction technique (VLEED) in the mode of total current spectroscopy. For F{sub 16}-CuPc films, the structure of the maxima in the total current spectra and its main differences from the structure of the maxima for the CuPc film are determined in the energy range from 5 to 15 eV abovemore » the Fermi level. The differences in the structure of vacant electron orbitals for CuPc and F{sub 16}-CuPc are also revealed using density functional theory calculations. As a result of an analysis of variations in the intensities of the total current spectra of the CuPc and F{sub 16}-CuPc films, it is assumed that an intermediate layer up to 1 nm thick appears during the formation of an interface between these films, which is characterized by a spread of the features in the total current spectrum. The height, width, and change in the work function are determined for the studied F{sub 16}-CuPc/NuPc interface barrier. A decrease in the level of vacuum by 0.7 eV occurs in the boundary region, which corresponds to electron density transfer from the CuPc film toward the F{sub 16}-CuPc substrate.« less

NO adsorption on Cu(110) and O(2 × 1)/Cu(110) surfaces from density functional theory calculations.

PubMed

Brión-Ríos, Antón X; Sánchez-Portal, Daniel; Cabrera-Sanfelix, Pepa

2016-04-14

In a recent study [M. Feng, et al., ACS Nano, 2011, 5, 8877], it was shown that CO molecules adsorbed on the quasi-one-dimensional O(2 × 1)/Cu(110) surface reconstruction tend to form highly-ordered single-molecule-wide rows along the direction perpendicular to the Cu-O chains. This stems from the peculiar tilted adsorption configuration of CO on this substrate, which gives rise to short-range attractive dipole-dipole interactions. Motivated by this observation, here we study the adsorption of nitric oxide (NO) on O(2 × 1)/Cu(110) and Cu(110) using density functional theory, with the aim of elucidating whether a similar behaviour can be expected for this molecule. We first study NO adsorption on a clean Cu(110) surface, where the role of short-range attractions between molecules has already been pointed out by the observation of the formation of NO dimers by scanning tunnelling microscopy [A. Shiotari, et al., Phys. Rev. Lett., 2011, 106, 156104]. On the clean Cu(110), the formation of dimers along the [110̄] direction is favourable, in agreement with published experimental results. However, the formation of extended NO rows is found to be unstable. Regarding the O(2 × 1)/Cu(110) substrate, we observe that NO molecules adsorb in between the Cu-O chains, causing a substantial disruption of the surface structure. Although individual molecules can be tilted with negligible energetic cost along the direction of the Cu-O chains, the interaction among neighbouring molecules was found to be repulsive along all directions and, consequently, the formation of dimers unfavourable.

Further differentiating item and order information in semantic memory: students' recall of words from the "CU Fight Song", Harry Potter book titles, and Scooby Doo theme song.

PubMed

Overstreet, Michael F; Healy, Alice F; Neath, Ian

2017-01-01

University of Colorado (CU) students were tested for both order and item information in their semantic memory for the "CU Fight Song". Following an earlier study by Overstreet and Healy [(2011). Item and order information in semantic memory: Students' retention of the "CU fight song" lyrics. Memory & Cognition, 39, 251-259. doi: 10.3758/s13421-010-0018-3 ], a symmetrical bow-shaped serial position function (with both primacy and recency advantages) was found for reconstructing the order of the nine lines in the song, whereas a function with no primacy advantage was found for recalling a missing word from each line. This difference between order and item information was found even though students filled in missing words without any alternatives provided and missing words came from the beginning, middle, or end of each line. Similar results were found for CU students' recall of the sequence of Harry Potter book titles and the lyrics of the Scooby Doo theme song. These findings strengthen the claim that the pronounced serial position function in semantic memory occurs largely because of the retention of order, rather than item, information.

Family Drawings before and after Treatment for Child Conduct Problems: Fluidity of Family Dysfunction.

PubMed

Kloft, Lilian; Hawes, David; Moul, Caroline; Sultan, Sonia; Dadds, Mark

2017-01-01

Children's drawings have previously been found to reflect their representations of family relationships. The present study examined whether evidence-based parent training for child conduct problems impacts on representations of family functioning using the Family Drawing Paradigm (FDP). N  = 53 clinic-referred children (aged 3-15) with conduct problems and their families were assessed pre-treatment and at 6-month follow-up on a modified version of the FDP. Analyses of changes in the FDP revealed improvements in family functioning but not tone of language (as indicated by written descriptors) following treatment. Higher family dysfunction scores were associated with increased levels of callous-unemotional (CU) traits in the children pre-treatment. Children with high levels of CU, however, demonstrated greater change in FDP dysfunction than a low CU group, resulting in similar levels at follow-up. CU traits also moderated the association between change in family warmth and conduct problem severity, with increased FDP warmth more strongly related to improved conduct problems in the high vs. the low CU group. FDP drawings are sensitive to changes in family functioning arising from parent training, accounting for unique variance in child outcomes independent of verbal reports.

Coverage dependent work function of graphene on a Cu(111) substrate with intercalated alkali metals

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

Cook, Brandon G.; Russakoff, Arthur; Varga, Kalman

2015-05-26

Using first-principles calculations, it is shown that the work function of graphene on copper can be adjusted by varying the concentration of intercalated alkali metals. Using density functional theory, we calculate the modulation of work function when Li, Na, or K are intercalated between graphene and a Cu(111) surface. Furthermore, the physical origins of the change in work function are explained in terms of phenomenological models accounting for the formation and depolarization of interfacial dipoles and the shift in the Fermi-level induced via charge transfer.

Unique helicase determinants in the essential conjugative TraI factor from Salmonella enterica serovar Typhimurium plasmid pCU1.

PubMed

McLaughlin, Krystle J; Nash, Rebekah P; Redinbo, Mathew R

2014-09-01

The widespread development of multidrug-resistant bacteria is a major health emergency. Conjugative DNA plasmids, which harbor a wide range of antibiotic resistance genes, also encode the protein factors necessary to orchestrate the propagation of plasmid DNA between bacterial cells through conjugative transfer. Successful conjugative DNA transfer depends on key catalytic components to nick one strand of the duplex DNA plasmid and separate the DNA strands while cell-to-cell transfer occurs. The TraI protein from the conjugative Salmonella plasmid pCU1 fulfills these key catalytic roles, as it contains both single-stranded DNA-nicking relaxase and ATP-dependent helicase domains within a single, 1,078-residue polypeptide. In this work, we unraveled the helicase determinants of Salmonella pCU1 TraI through DNA binding, ATPase, and DNA strand separation assays. TraI binds DNA substrates with high affinity in a manner influenced by nucleic acid length and the presence of a DNA hairpin structure adjacent to the nick site. TraI selectively hydrolyzes ATP, and mutations in conserved helicase motifs eliminate ATPase activity. Surprisingly, the absence of a relatively short (144-residue) domain at the extreme C terminus of the protein severely diminishes ATP-dependent strand separation. Collectively, these data define the helicase motifs of the conjugative factor TraI from Salmonella pCU1 and reveal a previously uncharacterized C-terminal functional domain that uncouples ATP hydrolysis from strand separation activity. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

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

PubMed

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

2016-04-27

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

C-H...Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu{sup I}Cu{sup II} coordination polymers

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

Shi Ling; Yang Ping; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510631

Two mixed-valence Cu{sup I}Cu{sup II} coordination polymers [Cu{sup I}Cu{sup II}(qdiol)ClL]{sub n} (qdiol{sup 2-}=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl{sub 2}, 1,4-dihydro-2,3-quinoxalinedione and L under the solvothermal condition. 1 and 2 are similar in composition, but differ remarkably in structure. The coordination modes of Cu{sup II}, qdiol{sup 2-} and L are identical in both complexes. But the Cu{sup I} ions are two- and three-coordinated, and the Cl{sup -} ions are terminal and bridging, in 1 and 2, respectively, which are relevant to the significantly different C-H...Cl hydrogen bonding pattern of bpy and phen. The temperaturemore » variable magnetic susceptibilities show that 1 is paramagnetic and 2 is weakly antiferromagnetic. The complex impedance spectroscopic studies indicate that both 1 and 2 are semiconductors and 2 is more conducting. - Graphical Abstract: Subtly different C-H...Cl bonding nature leads to diverse coordination modes and supramolecular networks, as well as physical properties of two Cu{sup I}Cu{sup II} coordination polymers with similar compositions. Highlights: > Two new Cu(I)-Cu(II) mixed-valence coordination polymers are obtained. > Environments of Cu(I) and Cl are different caused by C-H...Cl H-bonding. > Supramolecular networks are hence diverse. > Magnetic and semiconducting properties are influenced by the structures.« less

Oral treatment with Cu(II)(atsm) increases mutant SOD1 in vivo but protects motor neurons and improves the phenotype of a transgenic mouse model of amyotrophic lateral sclerosis.

PubMed

Roberts, Blaine R; Lim, Nastasia K H; McAllum, Erin J; Donnelly, Paul S; Hare, Dominic J; Doble, Philip A; Turner, Bradley J; Price, Katherine A; Lim, Sin Chun; Paterson, Brett M; Hickey, James L; Rhoads, Timothy W; Williams, Jared R; Kanninen, Katja M; Hung, Lin W; Liddell, Jeffrey R; Grubman, Alexandra; Monty, Jean-Francois; Llanos, Roxana M; Kramer, David R; Mercer, Julian F B; Bush, Ashley I; Masters, Colin L; Duce, James A; Li, Qiao-Xin; Beckman, Joseph S; Barnham, Kevin J; White, Anthony R; Crouch, Peter J

2014-06-04

Mutations in the metallo-protein Cu/Zn-superoxide dismutase (SOD1) cause amyotrophic lateral sclerosis (ALS) in humans and an expression level-dependent phenotype in transgenic rodents. We show that oral treatment with the therapeutic agent diacetyl-bis(4-methylthiosemicarbazonato)copper(II) [Cu(II)(atsm)] increased the concentration of mutant SOD1 (SOD1G37R) in ALS model mice, but paradoxically improved locomotor function and survival of the mice. To determine why the mice with increased levels of mutant SOD1 had an improved phenotype, we analyzed tissues by mass spectrometry. These analyses revealed most SOD1 in the spinal cord tissue of the SOD1G37R mice was Cu deficient. Treating with Cu(II)(atsm) decreased the pool of Cu-deficient SOD1 and increased the pool of fully metallated (holo) SOD1. Tracking isotopically enriched (65)Cu(II)(atsm) confirmed the increase in holo-SOD1 involved transfer of Cu from Cu(II)(atsm) to SOD1, suggesting the improved locomotor function and survival of the Cu(II)(atsm)-treated SOD1G37R mice involved, at least in part, the ability of the compound to improve the Cu content of the mutant SOD1. This was supported by improved survival of SOD1G37R mice that expressed the human gene for the Cu uptake protein CTR1. Improving the metal content of mutant SOD1 in vivo with Cu(II)(atsm) did not decrease levels of misfolded SOD1. These outcomes indicate the metal content of SOD1 may be a greater determinant of the toxicity of the protein in mutant SOD1-associated forms of ALS than the mutations themselves. Improving the metal content of SOD1 therefore represents a valid therapeutic strategy for treating ALS caused by SOD1. Copyright © 2014 the authors 0270-6474/14/348021-11$15.00/0.

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

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

Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.

2014-10-27

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI uponmore » reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.« less

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

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

Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.

2014-09-12

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI uponmore » reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.« less

Functionalized graphene oxide quantum dot-PVA hydrogel: a colorimetric sensor for Fe2+, Co2+ and Cu2+ ions

NASA Astrophysics Data System (ADS)

Baruah, Upama; Chowdhury, Devasish

2016-04-01

Functionalized graphene oxide quantum dots (GOQDs)-poly(vinyl alcohol) (PVA) hybrid hydrogels were prepared using a simple, facile and cost-effective strategy. GOQDs bearing different surface functional groups were introduced as the cross-linking agent into the PVA matrix thereby resulting in gelation. The four different types of hybrid hydrogels were prepared using graphene oxide, reduced graphene oxide, ester functionalized graphene oxide and amine functionalized GOQDs as cross-linking agents. It was observed that the hybrid hydrogel prepared with amine functionalized GOQDs was the most stable. The potential applicability of using this solid sensing platform has been subsequently explored in an easy, simple, effective and sensitive method for optical detection of M2+ (Fe2+, Co2+ and Cu2+) in aqueous media involving colorimetric detection. Amine functionalized GOQDs-PVA hybrid hydrogel when put into the corresponding solution of Fe2+, Co2+ and Cu2+ renders brown, orange and blue coloration respectively of the solution detecting the presence of Fe2+, Co2+ and Cu2+ ions in the solution. The minimum detection limit observed was 1 × 10-7 M using UV-visible spectroscopy. Further, the applicability of the sensing material was also tested for a mixture of co-existing ions in solution to demonstrate the practical applicability of the system. Insight into the probable mechanistic pathway involved in the detection process is also being discussed.

Sources of heavy metal pollution in agricultural soils of a rapidly industrializing area in the Yangtze Delta of China.

PubMed

Xu, Xianghua; Zhao, Yongcun; Zhao, Xiaoyan; Wang, Yudong; Deng, Wenjing

2014-10-01

The rapid industrialization and urbanization in developing countries have increased pollution by heavy metals, which is a concern for human health and the environment. In this study, 230 surface soil samples (0-20cm) were collected from agricultural areas of Jiaxing, a rapidly industrializing area in the Yangtze Delta of China. Sequential Gaussian simulation (SGS) and multivariate factorial kriging analysis (FKA) were used to identify and explore the sources of heavy metal pollution for eight metals (Cu, Zn, Pb, Cr, Ni, Cd, Hg and As). Localized hot-spots of pollution were identified for Cu, Zn, Pb, Cr, Ni and Cd with area percentages of 0.48 percent, 0.58 percent, 2.84 percent, 2.41 percent, 0.74 percent, and 0.68 percent, respectively. The areas with Hg pollution covered approximately 38 percent whereas no potential pollution risk was found for As. The soil parent material and point sources of pollution had significant influences on Cr, Ni, Cu, Zn and Cd levels, except for the influence of agricultural management practices also accounted for micro-scale variations (nugget effect) for Cu and Zn pollution. Short-range (4km) diffusion processes had a significant influence on Cu levels, although they did not appear to be the dominant sources of Zn and Cd variation. The short-range diffusion pollution arising from current and historic industrial emissions and urbanization, and long-range (33km) variations in soil parent materials and/or diffusion jointly determined the current concentrations of soil Pb. The sources of Hg pollution risk may be attributed to the atmosphere deposition of industrial emission and historical use of Hg-containing pesticides. Copyright © 2014 Elsevier Inc. All rights reserved.

Genetic variation in metallothionein and metal-regulatory transcription factor 1 in relation to urinary cadmium, copper, and zinc

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

Adams, Scott V., E-mail: sadams@fhcrc.org; Barrick, Brian; Christopher, Emily P.

Background: Metallothionein (MT) proteins play critical roles in the physiological handling of both essential (Cu and Zn) and toxic (Cd) metals. MT expression is regulated by metal-regulatory transcription factor 1 (MTF1). Hence, genetic variation in the MT gene family and MTF1 might influence excretion of these metals. Methods: 321 women were recruited in Seattle, WA and Las Cruces, NM and provided demographic information, urine samples for measurement of metal concentrations by mass spectrometry and creatinine, and blood or saliva for extraction of DNA. Forty-one single nucleotide polymorphisms (SNPs) within the MTF1 gene region and the region of chromosome 16 encodingmore » the MT gene family were selected for genotyping in addition to an ancestry informative marker panel. Linear regression was used to estimate the association of SNPs with urinary Cd, Cu, and Zn, adjusted for age, urinary creatinine, smoking history, study site, and ancestry. Results: Minor alleles of rs28366003 and rs10636 near the MT2A gene were associated with lower urinary Cd, Cu, and Zn. Minor alleles of rs8044719 and rs1599823, near MT1A and MT1B, were associated with lower urinary Cd and Zn, respectively. Minor alleles of rs4653329 in MTF1 were associated with lower urinary Cd. Conclusions: These results suggest that genetic variation in the MT gene region and MTF1 influences urinary Cd, Cu, and Zn excretion. - Highlights: • Genetic variation in metallothionein (MT) genes was assessed in two diverse populations. • Single nucleotide polymorphisms (SNPs) in MT genes were associated with mean urinary Cd, Cu and Zn. • Genetic variation may influence biomarkers of exposure, and associations of exposure with health.« less

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

PubMed Central

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

2010-01-01

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

INFLUENCE OF THE CHEMICAL POTENTIAL ON THE CARRIER EFFECTIVE MASS IN THE THERMOELECTRIC SOLID SOLUTION Cu2Zn1-xFexGeSe4

NASA Astrophysics Data System (ADS)

Zeier, Wolfgang G.; Day, Tristan; Schechtel, Eugen; Snyder, G. Jeffrey; Tremel, Wolfgang

2013-08-01

In this paper, we describe the synthesis and characterization of the solid solution Cu2Zn1-xFexGeSe4. Electronic transport data have been analyzed using a single parabolic band model and have been compared to Cu2+xZn1-xGeSe4. The effective mass of these undoped, intrinsically hole conducting materials increases linearly with increasing carrier concentration, showing a non-parabolic transport behavior within the valence band.