Measurement of labile copper in wine by medium exchange stripping potentiometry utilising screen printed carbon electrodes.

PubMed

Clark, Andrew C; Kontoudakis, Nikolaos; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R

2016-07-01

The presence of copper in wine is known to impact the reductive, oxidative and colloidal stability of wine, and techniques enabling measurement of different forms of copper in wine are of particular interest in understanding these spoilage processes. Electrochemical stripping techniques developed to date require significant pretreatment of wine, potentially disturbing the copper binding equilibria. A thin mercury film on a screen printed carbon electrode was utilised in a flow system for the direct analysis of labile copper in red and white wine by constant current stripping potentiometry with medium exchange. Under the optimised conditions, including an enrichment time of 500s and constant current of 1.0μA, the response range was linear from 0.015 to 0.200mg/L. The analysis of 52 red and white wines showed that this technique generally provided lower labile copper concentrations than reported for batch measurement by related techniques. Studies in a model system and in finished wines showed that the copper sulfide was not measured as labile copper, and that loss of hydrogen sulfide via volatilisation induced an increase in labile copper within the model wine system. Copyright © 2016 Elsevier B.V. All rights reserved.

Copper cladding on polymer surfaces by ionization-assisted deposition

NASA Astrophysics Data System (ADS)

Kohno, Tomoki; Tanaka, Kuniaki; Usui, Hiroaki

2018-03-01

Copper thin films were prepared on poly(ethylene terephthalate) (PET) and polyimide (PI) substrates by an ionization-assisted vapor deposition method. The films had a polycrystalline structure, and their crystallite size decreased with increasing ion acceleration voltage V a. Ion acceleration was effective in reducing the surface roughness of the films. Cross-sectional transmission electron microscopy revealed that the copper/polymer interface showed increased corrugation with increasing V a. The increase in V a also induced the chemical modification of polymer chains of the PET substrate, but the PI substrate underwent smaller modification after ion bombardment. Most importantly, the adhesion strength between the copper film and the PET substrate increased with increasing V a. It was concluded that ionization-assisted deposition is a promising technique for preparing metal clad layers on flexible polymer substrates.

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

NASA Astrophysics Data System (ADS)

Rhinow, Daniel; Hampp, Norbert A.

2012-06-01

Self-assembled monolayers (SAMs) of alkanethiols are major building blocks for nanotechnology. SAMs provide a functional interface between electrodes and biomolecules, which makes them attractive for biochip fabrication. Although gold has emerged as a standard, copper has several advantages, such as compatibility with semiconductors. However, as copper is easily oxidized in air, patterning SAMs on copper is a challenging task. In this work we demonstrate that submerged laser ablation (SLAB) is well-suited for this purpose, as thiols are exchanged in-situ, avoiding air exposition. Using different types of ω-substituted alkanethiols we show that alkanethiol SAMs on copper surfaces can be patterned using SLAB. The resulting patterns were analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Both methods indicate that the intense laser beam promotes the exchange of thiols at the copper surface. Furthermore, we present a procedure for the production of free-standing copper nanomembranes, oxidation-protected by alkanethiol SAMs. Incubation of copper-coated mica in alkanethiol solutions leads to SAM formation on both surfaces of the copper film due to intercalation of the organic molecules. Corrosion-protected copper nanomembranes were floated onto water, transferred to electron microscopy grids, and subsequently analyzed by electron energy loss spectroscopy (EELS).

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

DOE PAGES

Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna; ...

2015-06-25

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. In conclusion, the similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towardsmore » methanol, in both the enzyme system and copper-exchanged mordenite.« less

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

PubMed Central

Grundner, Sebastian; Markovits, Monica A.C.; Li, Guanna; Tromp, Moniek; Pidko, Evgeny A.; Hensen, Emiel J.M.; Jentys, Andreas; Sanchez-Sanchez, Maricruz; Lercher, Johannes A.

2015-01-01

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite. PMID:26109507

Potassium and the K+/H+ Exchanger Kha1p Promote Binding of Copper to ApoFet3p Multi-copper Ferroxidase*

PubMed Central

Wu, Xiaobin; Kim, Heejeong; Seravalli, Javier; Barycki, Joseph J.; Hart, P. John; Gohara, David W.; Di Cera, Enrico; Jung, Won Hee; Kosman, Daniel J.; Lee, Jaekwon

2016-01-01

Acquisition and distribution of metal ions support a number of biological processes. Here we show that respiratory growth of and iron acquisition by the yeast Saccharomyces cerevisiae relies on potassium (K+) compartmentalization to the trans-Golgi network via Kha1p, a K+/H+ exchanger. K+ in the trans-Golgi network facilitates binding of copper to the Fet3p multi-copper ferroxidase. The effect of K+ is not dependent on stable binding with Fet3p or alteration of the characteristics of the secretory pathway. The data suggest that K+ acts as a chemical factor in Fet3p maturation, a role similar to that of cations in folding of nucleic acids. Up-regulation of KHA1 gene in response to iron limitation via iron-specific transcription factors indicates that K+ compartmentalization is linked to cellular iron homeostasis. Our study reveals a novel functional role of K+ in the binding of copper to apoFet3p and identifies a K+/H+ exchanger at the secretory pathway as a new molecular factor associated with iron uptake in yeast. PMID:26966178

Characterization and copper binding properties of human COMMD1 (MURR1).

PubMed

Narindrasorasak, Suree; Kulkarni, Prasad; Deschamps, Patrick; She, Yi-Min; Sarkar, Bibudhendra

2007-03-20

COMMD1 (copper metabolism gene MURR1 (mouse U2af1-rs1 region1) domain) belongs to a family of multifunctional proteins that inhibit nuclear factor NF-kappaB. COMMD1 was implicated as a regulator of copper metabolism by the discovery that a deletion of exon 2 of COMMD1 causes copper toxicosis in Bedlington terriers. Here, we report the detailed characterization and specific copper binding properties of purified recombinant human COMMD1 as well as that of the exon 2 product, COMMD(61-154). By using various techniques including native-PAGE, EPR, UV-visible electronic absorption, intrinsic fluorescence spectroscopies as well as DEPC modification of histidines, we demonstrate that COMMD1 specifically binds copper as Cu(II) in 1:1 stoichiometry and does not bind other divalent metals. Moreover, the exon 2 product, COMMD(61-154), alone was able to bind Cu(II) as well as the wild type protein, with a stoichiometry of 1 mol of Cu(II) per protein monomer. The protection of DEPC modification of COMMD1 by Cu(II) implied that Cu(II) binding involves His residues. Further investigation by DEPC modification of COMMD(61-154) and subsequent MALDI MS mapping and MS/MS sequencing identified the protection of His101 and His134 residues in the presence of Cu(II). Fluorescence studies of single point mutants of the full-length protein revealed the involvement of M110 in addition to H134 in direct Cu(II) binding. Taken together, the data provide insight into the function of COMMD1 and especially COMMD(61-154), a product of exon 2 that is deleted in terriers affected by copper toxicosis, as a regulator of copper homeostasis.

Ionic Diffusion in Cu6PS5Br Studied by 63Cu NMR

NASA Astrophysics Data System (ADS)

Ohki, H.; Harazono, K.; Erata, T.; Tasaki, A.; Ikeda, R.

1993-10-01

Applying 63Cu NMR technique, we observed exchange between the nonequivalent copper sites in crystalline Cu6PS5Br, known as a member of the mineral "argyrodite". Below 200 K, where the motion of the copper (I) ion is slow, we could distinguish several nonequivalent copper sites. On increasing the temperature, the chemical exchange between the nonequivalent cation sites was seen on the 63Cu NMR spectra. We could determine the activation energy for this motion to be 35 kJ mol-1 , in good agreement with the published ionic conductivity.

Degradation of graphene coated copper in simulated proton exchange membrane fuel cell environment: Electrochemical impedance spectroscopy study

NASA Astrophysics Data System (ADS)

Ren, Y. J.; Anisur, M. R.; Qiu, W.; He, J. J.; Al-Saadi, S.; Singh Raman, R. K.

2017-09-01

Metallic materials are most suitable for bipolar plates of proton exchange membrane fuel cell (PEMFC) because they possess the required mechanical strength, durability, gas impermeability, acceptable cost and are suitable for mass production. However, metallic bipolar plates are prone to corrosion or they can passivate under PEMFC environment and interrupt the fuel cell operation. Therefore, it is highly attractive to develop corrosion resistance coating that is also highly conductive. Graphene fits these criteria. Graphene coating is developed on copper by chemical vapor deposition (CVD) with an aim to improving corrosion resistance of copper under PEMFC condition. The Raman Spectroscopy shows the graphene coating to be multilayered. The electrochemical degradation of graphene coated copper is investigated by electrochemical impedance spectroscopy (EIS) in 0.5 M H2SO4 solution at room temperature. After exposure to the electrolyte for up to 720 h, the charge transfer resistance (Rt) of the graphene coated copper is ∼3 times greater than that of the bare copper, indicating graphene coatings could improve the corrosion resistance of copper bipolar plates.

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

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

Caldwell, Andrew H.; Ha, Don-Hyung; Robinson, Richard D., E-mail: rdr82@cornell.edu

2014-10-28

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu{sub 1.81}S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ∼8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less

Annual Copper Mountain Conferences on Multigrid and Iterative Methods, Copper Mountain, Colorado

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

McCormick, Stephen F.

This project supported the Copper Mountain Conference on Multigrid and Iterative Methods, held from 2007 to 2015, at Copper Mountain, Colorado. The subject of the Copper Mountain Conference Series alternated between Multigrid Methods in odd-numbered years and Iterative Methods in even-numbered years. Begun in 1983, the Series represents an important forum for the exchange of ideas in these two closely related fields. This report describes the Copper Mountain Conference on Multigrid and Iterative Methods, 2007-2015. Information on the conference series is available at http://grandmaster.colorado.edu/~copper/.

A Robust Analytical Approach for the Identification of Specific Protein Carbonylation Sites: Metal-Catalyzed Oxidations of Human Serum Albumin

PubMed Central

Ugur, Zafer; Gronert, Scott

2017-01-01

The formation of protein carbonyls in the metal-catalyzed oxidation of human serum albumin (HSA) is characterized using a new analytical approach that involves tagging the modification site with multiple hydrazide reagents. Protein carbonyl formation at lysine and arginine residues was catalyzed with copper and iron ions, and the resulting oxidation patterns in HSA are contrasted. A total of 18 modification sites were identified with iron ion catalysis and 14 with copper ion catalysis. However, with the more stringent requirement of identification with at least two tagging reagents, the number of validated modification sites drops to 10 for iron and 9 for copper. Of the 14 total validated sites, there were only five in common for the two metal ions. The results illustrate the value of using multiple tagging agents and highlight the selective and specific nature of metal-catalyzed protein oxidations. PMID:28303033

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

PubMed

Gan, Patrick; Foord, John S; Compton, Richard G

2015-10-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.

Recycling of Cu powder from industrial sludge by combined acid leaching, chemical exchange and ferrite process.

PubMed

Tu, Yao-Jen; Chang, Chien-Kuei; You, Chen-Feng; Lou, Jie-Chung

2010-09-15

A method in combination of acid leaching, chemical exchange and ferrite process was applied to recycle copper and confer higher chemical stability to the sludge generated from etching process in printed circuit board industry. Ninety-five percent copper could be recycled in the form of powder from the sludge. Moreover, not only the wastewater after chemical exchange can be treated to fulfill the effluent standard, but also the sludge can satisfy the toxicity characteristic leaching procedure (TCLP) limits made by Taiwan's environmental protection administration. Copyright 2010 Elsevier B.V. All rights reserved.

Differential affinity of BsSCO for Cu(II) and Cu(I) suggests a redox role in copper transfer to the Cu(A) center of cytochrome c oxidase.

PubMed

Hill, Bruce C; Andrews, Diann

2012-06-01

SCO (synthesis of cytochrome c oxidase) proteins are involved in the assembly of the respiratory chain enzyme cytochrome c oxidase acting to assist in the assembly of the Cu(A) center contained within subunit II of the oxidase complex. The Cu(A) center receives electrons from the reductive substrate ferrocytochrome c, and passes them on to the cytochrome a center. Cytochrome a feeds electrons to the oxygen reaction site composed of cytochrome a(3) and Cu(B). Cu(A) consists of two copper ions positioned within bonding distance and ligated by two histidine side chains, one methionine, a backbone carbonyl and two bridging cysteine residues. The complex structure and redox capacity of Cu(A) present a potential assembly challenge. SCO proteins are members of the thioredoxin family which led to the early suggestion of a disulfide exchange function for SCO in Cu(A) assembly, whereas the copper binding capacity of the Bacillus subtilis version of SCO (i.e., BsSCO) suggests a direct role for SCO proteins in copper transfer. We have characterized redox and copper exchange properties of apo- and metalated-BsSCO. The release of copper (II) from its complex with BsSCO is best achieved by reducing it to Cu(I). We propose a mechanism involving both disulfide and copper exchange between BsSCO and the apo-Cu(A) site. This article is part of a Special Issue entitled: Biogenesis/Assembly of Respiratory Enzyme Complexes. Copyright © 2011 Elsevier B.V. All rights reserved.

High-resolution, cryogenic, side-entry type specimen stage

DOEpatents

King, Wayne E.; Merkle, Karl L.

1979-01-01

A high-resolution, cryogenic side-entry type specimen stage includes a copper block within which a specimen can be positioned in the electron beam of an electron microscope, one end of the copper block constituting a specimen heat exchanger, means for directing a flow of helium at cryogenic temperature into the heat exchanger, and electrical leads running from the specimen to the exterior of the microscope for four point D.C. electrical resistivity measurements.

Removal of copper by oxygenated pyrolytic tire char: kinetics and mechanistic insights.

PubMed

Quek, Augustine; Balasubramanian, Rajashekhar

2011-04-01

The kinetics of copper ion (Cu(II)) removal from aqueous solution by pyrolytic tire char was modeled using five different conventional models. A modification to these models was also developed through a modified equation that accounts for precipitation. Conventional first- and second-order reaction models did not fit the copper sorption kinetics well, indicating a lack of simple rate-order dependency on solute concentration. Instead, a reversible first-order rate reaction showed the best fit to the data, indicating a dependence on surface functional groups. Due to the varying solution pH during the sorption process, modified external and internal mass transfer models were employed. Results showed that the sorption of copper onto oxygenated chars was limited by external mass transfer and internal resistance with and without the modification. However, the modification of the sorption process produced very different results for unoxygenated chars, which showed neither internal nor external limitation to sorption. Instead, its slow sorption rate indicates a lack of surface functional groups. The sorption of Cu(II) by oxygenated and unoxygenated chars was also found to occur via three and two distinct stages, respectively. Copyright © 2010 Elsevier Inc. All rights reserved.

Cost-Effective Fabrication of Wettability Gradient Copper Surface by Screen Printing and its Application to Condensation Heat Transfer

NASA Astrophysics Data System (ADS)

Leu, Tzong-Shyng; Huang, Hung-Ming; Huang, Ding-Jun

2016-06-01

In this paper, wettability gradient pattern is applied to condensation heat transfer on a copper tube surface. For this application, the vital issue is how to fabricate gradient patterns on a curve tube surface to accelerate the droplet collection efficiently. For this purpose, novel fabrication processes are developed to form wettability gradient patterns on a curve copper tube surface by using roller screen printing surface modification techniques. The roller screen printing surface modification techniques can easily realize wettability gradient surfaces with superhydrophobicity and superhydrophilicity on a copper tube surface. Experimental results show the droplet nucleation sites, movement and coalescence toward the collection areas can be effectively controlled which can assist in removing the condensation water from the surface. The effectiveness of droplet collection is appropriate for being applied to condensation heat transfer in the foreseeable future.

An evaluation of a lathe-cut high-copper amalgam alloy.

PubMed

Knibbs, P J; Plant, C G; Shovelton, D S; Jones, P A

1987-09-01

Modification of an amalgam alloy may give rise to improved physical properties. The physical properties of a newly formulated, single-composition lathe-cut amalgam alloy were studied and found to be superior to those of a conventional lathe-cut amalgam alloy. However, such modification in formulation may result in changes in the clinical handling properties of the material. The high-copper amalgam alloy was assessed by a panel of general practitioners who found that the general handling properties of the material were similar to those of conventional lathe-cut amalgam alloys. The longer term performance of the high-copper alloy was assessed by means of a blind, controlled clinical trial carried out by two operators. A 1-year assessment of the resulting restorations and tooth replicas could not distinguish between the high-copper alloy and a conventional alloy. The two alloys had both given good clinical results.

Functional lignocellulosic material for the remediation of copper(II) ions from water: Towards the design of a wood filter.

PubMed

Vitas, Selin; Keplinger, Tobias; Reichholf, Nico; Figi, Renato; Cabane, Etienne

2018-05-09

In this study, the chemical modification of bulk beech wood is described along with its utilization as biosorbent for the remediation of copper from water. The material was prepared by esterification using anhydrides, and reaction conditions were optimized to propose a greener process, in particular by reducing the amount of solvent. This modification yields a lignocellulosic material whose native structure is preserved, with an increased amount of carboxylic groups (up to 3 mmol/g). We demonstrate that the material can remove up to 95% of copper from low concentration solutions (100- 500 ppm). The adsorption efficiency decreases with concentrated copper solutions, and we show that a limited number of -COOH groups participate in copper binding (ca. 0.1 Cu/-COOH). This result suggests a limited accessibility of -COOH groups in the wood scaffold. This was demonstrated by the characterization of -COOH and copper distributions inside wood. Raman and EDX imaging confirmed that most -COOH groups are located inside the wood cell walls, thereby limiting interactions with copper. According to this study, critical limitations of bulk wood as a biosorbent were identified, and the results will be used to improve the material and design an efficient wood filter for heavy metal remediation. Copyright © 2018 Elsevier B.V. All rights reserved.

Bioinspired conical copper wire with gradient wettability for continuous and efficient fog collection.

PubMed

Ju, Jie; Xiao, Kai; Yao, Xi; Bai, Hao; Jiang, Lei

2013-11-06

Inspired by the efficient fog collection on cactus spines, conical copper wires with gradient wettability are fabricated through gradient electrochemical corrosion and subsequent gradient chemical modification. These dual-gradient copper wires' fog-collection ability is demonstrated to be higher than that of conical copper wires with pure hydrophobic surfaces or pure hydrophilic surfaces, and the underlying mechanism is also analyzed. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of surface properties of copper-refractory metal alloys

DOEpatents

Verhoeven, John D.; Gibson, Edwin D.

1993-10-12

The surface properties of copper-refractory metal (CU-RF) alloy bodies are modified by heat treatments which cause the refractory metal to form a coating on the exterior surfaces of the alloy body. The alloys have a copper matrix with particles or dendrites of the refractory metal dispersed therein, which may be niobium, vanadium, tantalum, chromium, molybdenum, or tungsten. The surface properties of the bodies are changed from those of copper to that of the refractory metal.

Use of natural clinoptilolite for the removal of lead, copper and zinc in fixed bed column.

PubMed

Stylianou, Marinos A; Hadjiconstantinou, Michalis P; Inglezakis, Vasilis J; Moustakas, Konstantinos G; Loizidou, Maria D

2007-05-08

This work deals with the removal of lead, copper and zinc from aqueous solutions by using natural zeolite (clinoptilolite). Fixed bed experiments were performed, using three different volumetric flow rates of 5, 7 and 10bed volume/h, under a total normality of 0.01N, at initial pH of 4 and ambient temperature (25 degrees C). The removal efficiency increased when decreasing the flow rate and the following selectivity series was found: Pb(2+)>Zn(2+)> or =Cu(2+). Conductivity measurements showed that lead removal follows mainly ion exchange mechanism, while copper and zinc removal follows ion exchange and sorption mechanism as well.

Performance Analysis of Water Based Copper Oxide Nano Fluids in Heat Exchanger with Twisted Insert

NASA Astrophysics Data System (ADS)

Ashok Reddy, K.; Hanmanthu, Bhukya

2018-03-01

A new experimental setup has been designed for conducting experiments in a copper round pipe heat exchanger with inner diameter di=14.5mm and outer diameter do=16mm and length L = 1720 mm . By using two copper oxide nano concentrations of 0.1% and 0.3% with water as based fluid, the heat transfer rates have been obtained with helical twisted insert H/D=5 in turbulent flow condition. Reynolds number and friction factor with pressure gradient have been evaluated. The heat transfer rates of 0.1% conc. Nano-fluid with insert was found to be 13.77% more when compared to water.

Conformational exchange in pseudoazurin: different kinds of microsecond to millisecond dynamics characterized by their pH and buffer dependence using 15N NMR relaxation.

PubMed

Hass, Mathias A S; Vlasie, Monica D; Ubbink, Marcellus; Led, Jens J

2009-01-13

The dynamics of the reduced form of the blue copper protein pseudoazurin from Alcaligenes faecalis S-6 was investigated using (15)N relaxation measurements with a focus on the dynamics of the micro- to millisecond time scale. Different types of conformational exchange processes are observed in the protein on this time scale. At low pH, the protonation of the C-terminal copper-ligated histidine, His81, is observed. A comparison of the exchange rates in the presence and absence of added buffers shows that the protonation is the rate-limiting step at low buffer concentrations. This finding agrees with previous observations for other blue copper proteins, e.g., amicyanin and plastocyanin. However, in contrast to plastocyanin but similar to amicyanin, a second conformational exchange between different conformations of the protonated copper site is observed at low pH, most likely triggered by the protonation of His81. This process has been further characterized using CPMG dispersion methods and is found to occur with a rate of a few thousands per second. Finally, micro- to millisecond motions are observed in one of the loop regions and in the alpha-helical regions. These motions are unaffected by pH and are unrelated to the conformational changes in the active site of pseudoazurin.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

PubMed Central

Gan, Patrick; Foord, John S; Compton, Richard G

2015-01-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

Indirect photopatterning of functionalized organic monolayers via copper-catalyzed "click chemistry"

NASA Astrophysics Data System (ADS)

Williams, Mackenzie G.; Teplyakov, Andrew V.

2018-07-01

Solution-based lithographic surface modification of an organic monolayer on a solid substrate is attained based on selective area photo-reduction of copper (II) to copper (I) to catalyze the azide-alkyne dipolar cycloaddition "click" reaction. X-ray photoelectron spectroscopy is used to confirm patterning, and spectroscopic results are analyzed and supplemented with computational models to confirm the surface chemistry. It is determined that this surface modification approach requires irradiation of the solid substrate with all necessary components present in solution. This method requires only minutes of irradiation to result in spatial and temporal control of the covalent surface functionalization of a monolayer and offers the potential for wavelength tunability that may be desirable in many applications utilizing organic monolayers.

Exchange interaction between the triplet exciton and the localized spin in copper-phthalocyanine.

PubMed

Wu, Wei

2014-06-14

Triplet excitonic state in the organic molecule may arise from a singlet excitation and the following inter-system crossing. Especially for a spin-bearing molecule, an exchange interaction between the triplet exciton and the original spin on the molecule can be expected. In this paper, such exchange interaction in copper-phthalocyanine (CuPc, spin-½) was investigated from first-principles by using density-functional theory within a variety of approximations to the exchange correlation, ranging from local-density approximation to long-range corrected hybrid-exchange functional. The magnitude of the computed exchange interaction is in the order of meV with the minimum value (1.5 meV, ferromagnetic) given by the long-range corrected hybrid-exchange functional CAM-B3LYP. This exchange interaction can therefore give rise to a spin coherence with an oscillation period in the order of picoseconds, which is much shorter than the triplet lifetime in CuPc (typically tens of nanoseconds). This implies that it might be possible to manipulate the localized spin on Cu experimentally using optical excitation and inter-system crossing well before the triplet state disappears.

A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O.

PubMed

Danon, Albert; Saig, Avraham; Finkelstein, Yacov; Koresh, Jacob E

2005-11-10

Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.

Exploring scaling relations for chemisorption energies on transition-metal-exchanged zeolites ZSM-22 and ZSM-5

DOE PAGES

Siahrostami, Samira; Falsig, Hanne; Beato, Pablo; ...

2016-01-12

Copper exchange on all the different T sites of ZSM-22 and ZSM-5 is considered and the chemisorption energies of dioxygen, OH, and O species are studied. We show that for different T sites the adsorption energies vary significantly. The oxygen adsorption energy on copper-exchanged zeolites is quite similar to those of the most selective catalysts for oxidation reactions, that is, Ag and Au surfaces. The chemisorption energies of oxygen, carbon-, and nitrogen-containing species on different transition metals exchanged in ZSM-22 are also investigated. The study covers three different oxidation states, that is, 1+, 2+, and 3+ for the transition-metal exchanges.more » Scaling relations are presented for the corresponding species. Lastly, chemisorption of O scales with chemisorption of OH for all three considered exchanges, whereas there are essentially rough correlations for NH 2 and N as well as CH 3 and C.« less

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

PubMed Central

2016-01-01

The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Non-nucleoside building blocks for copper-assisted and copper-free click chemistry for the efficient synthesis of RNA conjugates.

PubMed

Jayaprakash, K N; Peng, Chang Geng; Butler, David; Varghese, Jos P; Maier, Martin A; Rajeev, Kallanthottathil G; Manoharan, Muthiah

2010-12-03

Novel non-nucleoside alkyne monomers compatible with oligonucleotide synthesis were designed, synthesized, and efficiently incorporated into RNA and RNA analogues during solid-phase synthesis. These modifications allowed site-specific conjugation of ligands to the RNA oligonucleotides through copper-assisted (CuAAC) and copper-free strain-promoted azide-alkyne cycloaddition (SPAAC) reactions. The SPAAC click reactions of cyclooctyne-oligonucleotides with various classes of azido-functionalized ligands in solution phase and on solid phase were efficient and quantitative and occurred under mild reaction conditions. The SPAAC reaction provides a method for the synthesis of oligonucleotide-ligand conjugates uncontaminated with copper ions.

Initial stage corrosion of nanocrystalline copper particles and thin films

NASA Astrophysics Data System (ADS)

Tao, Weimin

1997-12-01

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

Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells.

PubMed

Hattori, Shigeki; Wada, Yuji; Yanagida, Shozo; Fukuzumi, Shunichi

2005-07-06

The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N'](maleonitriledithiolato-S,S')copper ([Cu(SP)(mmt)])(0/)(-), bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)(2)](2+/+)), and bis(1,10-phenanthroline)copper ([Cu(phen)(2)](2+/+)) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)(2)](2+/+) < [Cu(SP)(mmt)](0/)(-) < [Cu(dmp)(2)](2+/+), in agreement with the order of the smaller structural change between the copper(II) and copper(I) complexes due to the distorted tetragonal geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I(3)(-)/I(-) couple. The light energy conversion efficiency (eta) values under illumination of simulated solar light irradiation (100 mW/cm(2)) of DSSCs using [Cu(phen)(2)](2+/+), [Cu(dmp)(2)](2+/+), and [Cu(SP)(mmt)](0/)(-) were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum eta value (2.2%) was obtained for a DSSC using the [Cu(dmp)(2)](2+/+) redox couple under the light irradiation of 20 mW/cm(2) intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I(3)(-)/I(-) couple.

77 FR 15169 - Self-Regulatory Organizations; NASDAQ OMX BX, Inc.; Notice of Filing and Immediate Effectiveness...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-14

... Exchange, including a 10Gb fiber connection, a 1Gb copper connection, and a 100 MB connection.\\4\\ In... enable its clients a more efficient connection to the Exchange. The Exchange proposes a 40G [sic] fiber... orders of 10Gb and 40Gb fiber connectivity to the Exchange completed between the effectiveness of this...

Exchange interaction between the triplet exciton and the localized spin in copper-phthalocyanine

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

Wu, Wei, E-mail: wei.wu@ucl.ac.uk

2014-06-14

Triplet excitonic state in the organic molecule may arise from a singlet excitation and the following inter-system crossing. Especially for a spin-bearing molecule, an exchange interaction between the triplet exciton and the original spin on the molecule can be expected. In this paper, such exchange interaction in copper-phthalocyanine (CuPc, spin-1/2 ) was investigated from first-principles by using density-functional theory within a variety of approximations to the exchange correlation, ranging from local-density approximation to long-range corrected hybrid-exchange functional. The magnitude of the computed exchange interaction is in the order of meV with the minimum value (1.5 meV, ferromagnetic) given by themore » long-range corrected hybrid-exchange functional CAM-B3LYP. This exchange interaction can therefore give rise to a spin coherence with an oscillation period in the order of picoseconds, which is much shorter than the triplet lifetime in CuPc (typically tens of nanoseconds). This implies that it might be possible to manipulate the localized spin on Cu experimentally using optical excitation and inter-system crossing well before the triplet state disappears.« less

Tryptophan 32 potentiates aggregation and cytotoxicity of a copper/zinc superoxide dismutase mutant associated with familial amyotrophic lateral sclerosis.

PubMed

Taylor, David M; Gibbs, Bernard F; Kabashi, Edor; Minotti, Sandra; Durham, Heather D; Agar, Jeffrey N

2007-06-01

One familial form of the neurodegenerative disease, amyotrophic lateral sclerosis, is caused by gain-of-function mutations in the gene encoding copper/zinc superoxide dismutase (SOD-1). This study provides in vivo evidence that normally occurring oxidative modification to SOD-1 promotes aggregation and toxicity of mutant proteins. The oxidation of Trp-32 was identified as a normal modification being present in both wild-type enzyme and SOD-1 with the disease-causing mutation, G93A, isolated from erythrocytes. Mutating Trp-32 to a residue with a slower rate of oxidative modification, phenylalanine, decreased both the cytotoxicity of mutant SOD-1 and its propensity to form cytoplasmic inclusions in motor neurons of dissociated mouse spinal cord cultures.

Effect of surface etching and electrodeposition of copper on nitinol

NASA Astrophysics Data System (ADS)

Ramos-Moore, E.; Rosenkranz, A.; Matamala, L. F.; Videla, A.; Durán, A.; Ramos-Grez, J.

2017-10-01

Nitinol-based materials are very promising for medical and dental applications since those materials can combine shape memory, corrosion resistance, biocompatibility and antibacterial properties. In particular, surface modifications and coating deposition can be used to tailor and to unify those properties. We report preliminary results on the study of the effect of surface etching and electrodeposition of Copper on Nitinol using optical, chemical and thermal techniques. The results show that surface etching enhances the surface roughness of Nitinol, induces the formation of Copper-based compounds at the Nitinol-Copper interface, reduces the austenitic-martensitic transformations enthalpies and reduces the Copper coating roughness. Further studies are needed in order to highlight the influence of the electrodeposited Copper on the memory shape properties of NiTi.

Rapid Analysis of Copper Ore in Pre-Smelter Head Flow Slurry by Portable X-ray Fluorescence.

PubMed

Burnett, Brandon J; Lawrence, Neil J; Abourahma, Jehad N; Walker, Edward B

2016-05-01

Copper laden ore is often concentrated using flotation. Before the head flow slurry can be smelted, it is important to know the concentration of copper and contaminants. The concentration of copper and other elements fluctuate significantly in the head flow, often requiring modification of the concentrations in the slurry prior to smelting. A rapid, real-time analytical method is needed to support on-site optimization of the smelter feedstock. A portable, handheld X-ray fluorescence spectrometer was utilized to determine the copper concentration in a head flow suspension at the slurry origin. The method requires only seconds and is reliable for copper concentrations of 2.0-25%, typically encountered in such slurries. © The Author(s) 2016.

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films

NASA Astrophysics Data System (ADS)

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J.; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G.; Headrick, Randall L.; McGill, Stephen A.; Furis, Madalina I.

2015-11-01

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ - d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of -4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials.

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films

PubMed Central

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J.; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G.; Headrick, Randall L.; McGill, Stephen A.; Furis, Madalina I.

2015-01-01

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ − d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of −4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials. PMID:26559337

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films.

PubMed

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G; Headrick, Randall L; McGill, Stephen A; Furis, Madalina I

2015-11-12

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ - d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of -4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials.

Numerical investigation of forced convection of nano fluid flow in horizontal U-longitudinal finned tube heat exchanger

NASA Astrophysics Data System (ADS)

Qasim, S. M.; Sahar, A. F. A.; Firas, A. A.

2015-11-01

A numerical study has been carried out to investigate the heat transfer by laminar forced convection of nanofluid taking Titania (TiO2) and Alumina (Al2O3) as nanoparticles and the water as based fluid in a three dimensional plain and U-longitudinal finned tube heat exchanger. A Solid WORKS PREMIUM 2012 is used to draw the geometries of plain tube heat exchanger or U-longitudinal copper finned tube heat exchanger. Four U-longitudinal copper fins have 100 cm long, 3.8cm height and 1mm thickness are attached to a straight copper tube of 100 cm length, 2.2 cm inner diameter and 2.39 cm outer diameter. The governing equations which used as continuity, momentum and energy equations under assumptions are utilized to predict the flow field, temperature distribution, and heat transfer of the heat exchanger. The finite volume approach is used to obtain all the computational results using commercial ANSYS Fluent copy package 14.0 with assist of solid works and Gambit software program. The effect of various parameters on the performance of heat exchanger are investigated numerically such as Reynolds' number (ranging from 270 to 1900), volume consternation of nanoparticles (0.2%, 0.4%, 0.6%, 0.8%), type of nanoparticles, and mass flow rate of nanofluid in the hot region of heat exchanger. For 0.8% consternation of nanoparticles, heat transfer has significant enhancement in both nanofluids. It can be found about 7.3% for TiO2 and about 7.5% for Al2O3 compared with the water only as a working fluid.

Solar heating and hot water system installed at Arlington Raquetball Club, Arlington, Virginia

NASA Technical Reports Server (NTRS)

1981-01-01

A solar space and water heating system is described. The solar energy system consists of 2,520 sq. ft. of flat plate solar collectors and a 4,000 gallon solar storage tank. The transfer medium in the forced closed loop is a nontoxic antifreeze solution (50 percent water, 50 percent propylene glycol). The service hot water system consists of a preheat coil (60 ft. of 1 1/4 in copper tubing) located in the upper third of the solar storage tank and a recirculation loop between the preheat coil and the existing electric water heaters. The space heating system consists of two separate water to air heat exchangers located in the ducts of the existing space heating/cooling systems. The heating water is supplied from the solar storage tank. Extracts from site files, specification references for solar modifications to existing building heating and hot water systems, and installation, operation and maintenance instructions are included.

Effect of copper on the properties of Pr-Dy-Fe-Co-B sintered magnets

NASA Astrophysics Data System (ADS)

Kablov, E. N.; Piskorskii, V. P.; Valeev, R. A.; Volkov, N. V.; Davydova, E. A.; Shaikhutdinov, K. A.; Balaev, D. A.; Semenov, S. V.

2014-01-01

The effect of copper on the properties of magnets (Pr0.52Dy0.48)13(Fe65Co0.35)80.3 - x Cu x B6.7 ( x = 0-10) has been studied. Alloying with copper is shown to decrease the sintering temperature and to increase the content of the principal (Pr,Dy)2(Fe,Co)14B magnetic phase. For compositions with x = 1.3-3.3, copper is found to affect the value and sign of the temperature induction coefficient (TIC). It is shown that the effect of copper on the TIC is determined by the substitution of copper ions for iron ions in lattice sites, which are coupled via an antiferromagnetic exchange interaction.

Influence of indigenous and added iron on copper extraction from soil.

PubMed

Di Palma, Luca

2009-10-15

Experimental tests of copper leaching from a low permeability soil are presented and discussed. The objective of the experiments was to investigate the influence of indigenous and added iron in the soil towards copper mobilization. Metals' leaching was performed by flushing (column tests) or washing (batch tests) the soil with an aqueous solution of ethylenediaminetetraacetic acid, EDTA. An excess of EDTA was used in flushing tests (up to a EDTA:Cu molar ratio of about 26.2:1), while, in washing tests, the investigated EDTA vs. copper molar ratios were in the range between 1 (equimolar tests) and 8. Copper extraction yield in flushing tests (up to about 85%) was found to depend upon contact time between the soil and the leaching solution and the characteristics of the conditioning solution. The saturation of the soil with a NaNO(3) solution before the treatment, favoured the flushing process reducing the time of percolation, but resulted in a lower metal extraction during the following percolation of EDTA. The indigenous iron was competitive with copper to form EDTA complexes only when it was present in the organic and oxides-hydroxides fractions. Artificial iron addition to the soil resulted in an increase of both the exchangeable iron and the iron bonded to the organic fraction of the soil, thus increasing the overall amount of iron available to extraction. In both batch and continuous tests, the mechanism of copper extraction was found to involve the former dissolution of metal salts, that lead to an initial high concentration of both copper and selected competitive cations (essentially Ca(2+)), and the following EDTA exchange reaction between calcium and copper complexes. The initial metal salts dissolution was found to be pH-dependant.

Copper(I)-catalyzed substitution reactions of propargylic amines: importance of C(sp)-C(sp3) bond cleavage in generation of iminium intermediates.

PubMed

Sugiishi, Tsuyuka; Kimura, Akifumi; Nakamura, Hiroyuki

2010-04-21

Substitution reactions of propargylic amines proceed in the presence of copper(I) catalysts. Mechanistic studies showed that C(sp)-C(sp(3)) bond cleavage assisted by nitrogen lone-pair electrons is essential for the reaction, and the resulting iminium intermediates undergo amine exchange, aldehyde exchange, and alkyne addition reactions. Because iminium intermediates are key to aldehyde-alkyne-amine (A(3)) coupling reactions, this transformation is effective not only for reconstruction of propargylic amines but also for chiral induction of racemic compounds in the presence of chiral catalysts.

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

MODIFICATIONS TO REDUCE DRAG OUT AT A PRINTED CIRCUIT BOARD MANUFACTURER

EPA Science Inventory

This MnTAP/EPA Waste Reduction Innovative Technology Evaluation project at Micom, Inc., demonstrated the waste reducing capability of two simple rinsing modifications on an etchant and an electroless copper process. he simple, tow (or no) cost, low technology changes that were ma...

The influence of flow modification on air and PCM temperatures in an accumulative heat exchanger

NASA Astrophysics Data System (ADS)

Borcuch, Marcin; Musiał, Michał; Sztekler, Karol; Kalawa, Wojciech; Gumuła, Stanisław; Stefański, Sebastian

2018-06-01

The paper presents the influence of flow modification on the operation of an accumulative heat exchanger. This device can be used as a regenerator in ventilation and air supply systems. A heat exchanger uses ceresine (a mixture of paraffins) as a phase change material (PCM). The aim of this research was to determine the effect of flow modification on temperature distribution and pressure drops in the device. The introduction contains a short description of the test stand used, including the accumulative heat exchanger, the guide vanes, and the locations of measurement and control equipment. We found that additional objects limited vortex structures, increased the inside temperature, and dropped the pressure along the heat exchanger. Guidelines for further research are proposed and briefly discussed.

Synthesis and characterization of nanocrystalline mordenite, high silica zeolite RHO, and copper faujasite

NASA Astrophysics Data System (ADS)

Hincapie Palacio, Beatriz Omaira

Mordenite is a zeolite that has been used as a selective adsorbent and as a catalyst. In reactions where the diffusion of reagents into the pore system is the rate-determining step, nanoparticles of the catalyst improve the reaction rate. Mordenite with a crystal diameter smaller than 100 nm has been prepared by the modification of different synthetic parameters such as the source of aluminum, the presence of seeds, the use of low temperatures (150°C vs. 170°C), longer crystallization times (24 h vs. 96 h), and different silica to alumina ratios (10--30). The decrease in the crystal diameter of the prepared mordenite was monitored by the application of the Scherrer equation that relates the broadness of the X-ray diffraction peaks to crystal sizes. Zeolite RHO with an initial silica to alumina ratio (SAR) higher than 20 has been prepared. EDTA, citric acid, and tartaric acid have been used as complexing agents in the synthesis of zeolite RHO. Crystallization time increases (from 48 h to 900 h) with increasing the silica to alumina ratios (SAR) of the initial gel (SAR: 10.8 to 30) and by adding complexing agents. Complexing agents favor the formation of small crystals (0.8 mum) with increased silica to alumina ratio (final SAR: 4.5 vs. 4.0 without complexing agents). The products were characterized by XRD, FESEM, EDX, FTIR, and in-situ XRD. Copper containing faujasite has been successfully prepared for the first time using a direct synthesis method. Ammonium hydroxide was used to form a copper complex that was later mixed with the reacting gel. Crystallization took place at 85°C for 11 days. The copper containing faujasite obtained was characterized by XRD, FESEM, EDX, EPR, FTIR, TPR, and BET. According to the XRD pattern only FAU type zeolite was obtained. According to TPR experiments, the reduction temperature for Cu2+ ions present in Cu-FAU prepared by direct synthesis was 70 K higher than for Cu-FAU prepared by ion-exchange. This difference can be due to the different location of the copper ions in the supercages or in the sodalite cages of the faujasite.

A spin-frustrated trinuclear copper complex based on triaminoguanidine with an energetically well-separated degenerate ground state.

PubMed

Spielberg, Eike T; Gilb, Aksana; Plaul, Daniel; Geibig, Daniel; Hornig, David; Schuch, Dirk; Buchholz, Axel; Ardavan, Arzhang; Plass, Winfried

2015-04-06

We present the synthesis and crystal structure of the trinuclear copper complex [Cu3(saltag)(bpy)3]ClO4·3DMF [H5saltag = tris(2-hydroxybenzylidene)triaminoguanidine; bpy = 2,2'-bipyridine]. The complex crystallizes in the trigonal space group R3̅, with all copper ions being crystallographically equivalent. Analysis of the temperature dependence of the magnetic susceptibility shows that the triaminoguanidine ligand mediates very strong antiferromagnetic interactions (JCuCu = -324 cm(-1)). Detailed analysis of the magnetic susceptibility and magnetization data as well as X-band electron spin resonance spectra, all recorded on both powdered samples and single crystals, show indications of neither antisymmetric exchange nor symmetry lowering, thus indicating only a very small splitting of the degenerate S = (1)/2 ground state. These findings are corroborated by density functional theory calculations, which explain both the strong isotropic and negligible antisymmetric exchange interactions.

A two-cell chamber for measuring gas exchange in tree seedlings

Treesearch

Keith F. Jensen; Frederick W. Bender; Roberta G. Masters

1973-01-01

A two-celled chamber for measuring gas exchange in tree seedlings is described. Temperature is controlled within ± 0.5º C by means of a copper coil. The two cells are independent of one another, and one cell can be used as a preconditioning cell while gas exchange measurements are being made in the second cell.

Systems biology approach in Chlamydomonas reveals connections between copper nutrition and multiple metabolic steps.

PubMed

Castruita, Madeli; Casero, David; Karpowicz, Steven J; Kropat, Janette; Vieler, Astrid; Hsieh, Scott I; Yan, Weihong; Cokus, Shawn; Loo, Joseph A; Benning, Christoph; Pellegrini, Matteo; Merchant, Sabeeha S

2011-04-01

In this work, we query the Chlamydomonas reinhardtii copper regulon at a whole-genome level. Our RNA-Seq data simulation and analysis pipeline validated a 2-fold cutoff and 10 RPKM (reads per kilobase of mappable length per million mapped reads) (~1 mRNA per cell) to reveal 63 CRR1 targets plus another 86 copper-responsive genes. Proteomic and immunoblot analyses captured 25% of the corresponding proteins, whose abundance was also dependent on copper nutrition, validating transcriptional regulation as a major control mechanism for copper signaling in Chlamydomonas. The impact of copper deficiency on the expression of several O₂-dependent enzymes included steps in lipid modification pathways. Quantitative lipid profiles indicated increased polyunsaturation of fatty acids on thylakoid membrane digalactosyldiglycerides, indicating a global impact of copper deficiency on the photosynthetic apparatus. Discovery of a putative plastid copper chaperone and a membrane protease in the thylakoid suggest a mechanism for blocking copper utilization in the chloroplast. We also found an example of copper sparing in the N assimilation pathway: the replacement of copper amine oxidase by a flavin-dependent backup enzyme. Forty percent of the targets are previously uncharacterized proteins, indicating considerable potential for new discovery in the biology of copper.

Fabrication of high wettability gradient on copper substrate

NASA Astrophysics Data System (ADS)

Huang, Ding-Jun; Leu, Tzong-Shyng

2013-09-01

Copper is one of the most widely used materials in condensation heat transfer. Recently there has been great interest in improving the condensation heat transfer efficiency through copper surface modification. In this study, we describe the fabrication processes of how copper surfaces were modified to be superhydrophilic (CA ≤ 10°) and superhydrophobic (CA > 150°) by means of H2O2 immersion and fluorination with Teflon. The wettability gradient of copper surfaces with contact angles (CA) changing from superhydrophilic to superhydrophobic are also demonstrated. Unlike previous studies on gradient surfaces in which the wettability gradient is controlled either non-precisely or entirely uncontrolled, in this study, the contact angles along wettability gradient copper surfaces vary with a precisely designed gradient. It is demonstrated that a high wettability gradient copper surface can be successfully fabricated using photolithography to define the area ratios between superhydrophilic and superhydrophobic patterns within a short distance. The fabricated wettability gradient of copper surfaces is expected to be able to enhance the condensation heat transfer efficiency.

Modelling copper-phthalocyanine/cobalt-phthalocyanine chains: towards magnetic quantum metamaterials.

PubMed

Wu, Wei

2014-07-23

The magnetic properties of a theoretically designed molecular chain structure CuCoPc2, in which copper-phthalocyanine (CuPc) and cobalt-phthalocyanine (CoPc) alternate, have been investigated across a range of chain structures. The computed exchange interaction for the α-phase CuCoPc2 is ∼ 5 K (ferromagnetic), in strong contrast to the anti-ferromagnetic interaction recently observed in CuPc and CoPc. The computed exchange interactions are strongly dependent on the stacking angle but weakly on the sliding angle, and peak at 20 K (ferromagnetic). These ferromagnetic interactions are expected to arise from direct exchange with the strong suppression of super-exchange interaction. These first-principles calculations show that π-conjugated molecules, such as phthalocyanine, could be used as building blocks for the design of magnetic materials. This therefore extends the concept of quantum metamaterials further into magnetism. The resulting new magnetic materials could find applications in the studies such as organic spintronics.

Hydrothermal synthesis of copper zirconium phosphate hydrate [Cu(OH)2Zr(HPO4)2·2H2O] and an investigation of its lubrication properties in grease.

PubMed

Zhang, Xiaosheng; Xu, Hong; Zuo, Zhijun; Lin, Zhi; Ferdov, Stanislav; Dong, Jinxiang

2013-08-28

Copper zirconium phosphate hydrate (Cu(OH)2Zr(HPO4)2·2H2O, hereafter referred to as Cu-α-ZrP) with high crystallinity was directly synthesized in a NaF-CuO-ZrO-P2O5-H2O system under hydrothermal conditions. The copper ion was confirmed to be an exchangeable cation in the Cu-α-ZrP through elemental analysis and a proton ion exchange process. The crystal structure of the Cu-α-ZrP was determined ab initio by using X-ray powder diffraction data. In the structure, the CuO6 octahedron would be located in an exchangeable atom position. Moreover, Cu-α-ZrP was evaluated as an additive in grease in a four ball test. The maximum nonseizure load (PB, representing the load-carrying capacity) of the base grease containing Cu-α-ZrP was increased from 353 to 1235 N. The excellent load-carrying capacity may be explained by the easier adherence of the material to the worn surface forming a tight protective film.

Wire-packed heat exchangers for dilution refrigerators.

PubMed

Polturak, E; Rappaport, M; Rosenbaum, R

1978-03-01

Very simple wire-packed step heat exchangers for dilution refrigerators are described. No sintering is used in fabrication. Flow impedances and thermal resistance between the liquid and the copper wires are low. A refrigerator with five wire-packed heat exchangers in addition to a countercurrent heat exchanger attains a temperature of 11.4 mK with a single mixing chamber and 6.1 mK with two mixing chambers. High cooling power is achieved at modest (3)He circulation rates.

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

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

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

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

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

PubMed

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

2017-09-01

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

Repetitive switching for an electromagnetic rail gun

NASA Astrophysics Data System (ADS)

Gruden, J. M.

1983-12-01

Previous testing on a repetitive opening switch for inductive energy storage has proved the feasibility of the rotary switch concept. The concept consists of a rotating copper disk (rotor) with a pie-shaped insulator section and brushes which slide along each of the rotor surfaces. While on top of the copper surface, the brushes and rotor conduct current allowing the energy storage inductor to charge. When the brushes slide onto the insulator section, the current cannot pass through the rotor and is diverted into the load. This study investigates two new brush designs and a rotor modification designed to improve the current commutating capabilities of the switch. One brush design (fringe fiber) employs carbon fibers on the leading and trailing edge of the brush to increase the resistive commutating action as the switch opens and closes. The other brush design uses fingers to conduct current to the rotor surface, effectively increasing the number of brush contact points. The rotor modification was the placement of tungsten inserts at the copper-insulator interfaces.

Crosslinked anion exchange membranes prepared from poly(phenylene oxide) (PPO) for non-aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Li, Yun; Sniekers, Jeroen; Malaquias, João C.; Van Goethem, Cedric; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F. J.

2018-02-01

A stable and eco-friendly anion-exchange membrane (AEM) was prepared and applied in a non-aqueous all-copper redox flow battery (RFB). The AEM was prepared via a simple procedure, leading to a cross-linked structure containing quaternary ammonium groups without involvement of harmful trimethylamine. A network was thus constructed which ensured both ion transport and solvent resistance. The ion exchange capacity (IEC) of the membrane was tuned from 0.49 to 1.03 meq g-1 by varying the content of the 4, 4‧-bipyridine crosslinking agent. The membrane showed a good anion conductivity and retention of copper ions. As a proof of principle, a RFB single cell with this crosslinked membrane yielded a coulombic efficiency of 89%, a voltage efficiency of 61% and an energy efficiency of 54% at 7.5 mA cm-2.

Periodate and hypobromite modification of Southern pine wood to improve sorption of copper ion

Treesearch

James D. McSweeny; Roger M. Rowell; George C. Chen; Thomas L. Eberhardt; Min Soo-Hong

2008-01-01

Milled southern pine wood was modified with sequential treatments of sodium periodate and sodium hypobromite for the purpose of improving copper ion (Cu2+) sorption capacity of the wood when tested in 24-h equilibrium batch tests. The modified wood provided additional carboxyl groups to those in the native wood and substantially increased Cu2+ uptake over that of...

Effect of citric acid modification of aspen wood on sorption of copper ion

Treesearch

James D. McSweeny; Roger M. Rowell; Soo Hong Min

2006-01-01

Milled aspen wood was thermochemically modified with citric acid for the purpose of improving the copper (Cu2+) ion sorption capacity of the wood when tested in 24-hour equilibrium batch tests. The wood-citric acid adducts provided additional carboxyl groups to those in the native wood and substantially increased Cu2+ ion uptake of the modified wood compared with that...

Effect of copper sulphate treatment on natural phytoplanktonic communities.

PubMed

Le Jeune, Anne-Hélène; Charpin, Marie; Deluchat, Véronique; Briand, Jean-François; Lenain, Jean-François; Baudu, Michel; Amblard, Christian

2006-12-01

Copper sulphate treatment is widely used as a global and empirical method to remove or control phytoplankton blooms without precise description of the impact on phytoplanktonic populations. The effects of two copper sulphate treatments on natural phytoplanktonic communities sampled in the spring and summer seasons, were assessed by indoor mesocosm experiments. The initial copper-complexing capacity of each water sample was evaluated before each treatment. The copper concentrations applied were 80 microg l(-1) and 160 microg l(-1) of copper, below and above the water complexation capacity, respectively. The phytoplanktonic biomass recovered within a few days after treatment. The highest copper concentration, which generated a highly toxic environment, caused a global decrease in phytoplankton diversity, and led to the development and dominance of nanophytoplanktonic Chlorophyceae. In mesocosms treated with 80 microg l(-1) of copper, the effect on phytoplanktonic community size-class structure and composition was dependent on seasonal variation. This could be related to differences in community composition, and thus to species sensitivity to copper and to differences in copper bioavailability between spring and summer. Both treatments significantly affected cyanobacterial biomass and caused changes in the size-class structure and composition of phytoplanktonic communities which may imply modifications of the ecosystem structure and function.

Systems Biology Approach in Chlamydomonas Reveals Connections between Copper Nutrition and Multiple Metabolic Steps[C][W][OA

PubMed Central

Castruita, Madeli; Casero, David; Karpowicz, Steven J.; Kropat, Janette; Vieler, Astrid; Hsieh, Scott I.; Yan, Weihong; Cokus, Shawn; Loo, Joseph A.; Benning, Christoph; Pellegrini, Matteo; Merchant, Sabeeha S.

2011-01-01

In this work, we query the Chlamydomonas reinhardtii copper regulon at a whole-genome level. Our RNA-Seq data simulation and analysis pipeline validated a 2-fold cutoff and 10 RPKM (reads per kilobase of mappable length per million mapped reads) (~1 mRNA per cell) to reveal 63 CRR1 targets plus another 86 copper-responsive genes. Proteomic and immunoblot analyses captured 25% of the corresponding proteins, whose abundance was also dependent on copper nutrition, validating transcriptional regulation as a major control mechanism for copper signaling in Chlamydomonas. The impact of copper deficiency on the expression of several O2-dependent enzymes included steps in lipid modification pathways. Quantitative lipid profiles indicated increased polyunsaturation of fatty acids on thylakoid membrane digalactosyldiglycerides, indicating a global impact of copper deficiency on the photosynthetic apparatus. Discovery of a putative plastid copper chaperone and a membrane protease in the thylakoid suggest a mechanism for blocking copper utilization in the chloroplast. We also found an example of copper sparing in the N assimilation pathway: the replacement of copper amine oxidase by a flavin-dependent backup enzyme. Forty percent of the targets are previously uncharacterized proteins, indicating considerable potential for new discovery in the biology of copper. PMID:21498682

Effect of chemical pollution on forms of 137Cs, 90Sr and 239,240Pu in arctic soil studied by sequential extraction.

PubMed

Puhakainen, M; Riekkinen, I; Heikkinen, T; Jaakkola, T; Steinnes, E; Rissanen, K; Suomela, M; Thørring, H

2001-01-01

The aim of the present study was to determine the forms of 137Cs, 90Sr and 239,240Pu occurring in different soil horizons using sequential extraction of samples taken from four sites located along a pollution gradient from the copper-nickel smelter at Monchegorsk in the Kola Peninsula, Russia, and from a reference site in Finnish Lapland in 1997. A selective sequential-leaching procedure was employed using a modification of the method of Tessier, Cambell and Bisson ((1979). Analytical Chemistry, 51, 844-851). For 137Cs the organic (O) and uppermost mineral (E1) layer were studied, for 90Sr and 239,240Pu only the uppermost organic layer (Of). The fraction of 137Cs occurring in readily exchangeable form in the organic layer was about 50% at the reference site and decreased as a function of pollution, being 15% at the most polluted site in the Kola Peninsula. There was a clear positive correlation in the O layer between the distance from the smelter and the percentage of 137Cs extracted in the readily exchangeable fraction (Spearman correlation rsp = 0.7805, p = 0.0001), whereas in the E1 layer no correlation was evident. The distribution of 90Sr in the Of layer was similar at all sites, with the highest amounts occurring in exchangeable form and bound to organic matter, whereas stable Sr showed a somewhat different distribution with the highest amount in the oxide fraction. Most of the 239,240Pu was bound to organic matter. Chemical pollution affected the exchangeable fraction of 239,240Pu, which was about 1% at the most polluted site and 4-6% at the other sites.

The role of arbuscular mycorrhiza on change of heavy metal speciation in rhizosphere of maize in wastewater irrigated agriculture soil.

PubMed

Huang, Yi; Tao, Shu; Chen, You-jian

2005-01-01

To understand the roles of mycorrhiza in metal speciation in the rhizosphere and the impact on increasing host plant tolerance against excessive heavy metals in soil, maize (Zea mays L.) inoculated with arbuscular mycorrhizal fungus (Glomus mosseae) was cultivated in heavy metal contaminated soil. Speciations of copper, zinc and lead in the soil were analyzed with the technique of sequential extraction. The results showed that, in comparison to the bolked soil, the exchangeable copper increased from 26% to 43% in non-infected and AM-infected rhizoshpere respectively; while other speciation (organic, carbonate and Fe-Mn oxide copper) remained constant and the organic bound zinc and lead also increased but the exchangeable zinc and lead were undetectable. The organic bound copper, zinc and lead were higher by 15%, 40% and 20%, respectively, in the rhizosphere of arbuscular mycorrhiza infected maize in comparison to the non-infected maize. The results might indicate that mycorrhiza could protect its host plants from the phytotoxicity of excessive copper, zinc and lead by changing the speciation from bio-available to the non-bio-available form. The fact that copper and zinc accumulation in the roots and shoots of mycorrhia infected plants were significantly lower than those in the non-infected plants might also suggest that mycorrhiza efficiently restricted excessive copper and zinc absorptions into the host plants. Compared to the non-infected seedlings, the lead content of infected seedlings was 60% higher in shoots. This might illustrate that mycorrhiza have a different mechanism for protecting its host from excessive lead phytotoxicity by chelating lead in the shoots.

Two band model for the cuprates

NASA Astrophysics Data System (ADS)

Liu, Shiu; White, Steven

2009-03-01

We use a numerical canonical transformation approach to derive an effective two-band model for the hole-doped cuprates, which keeps both oxygen and copper orbitals but removes double occupancy from each. A similar model was considered previously by Frenkel, Gooding, Shraiman, and Siggia (PRB 41, number 1, page 350). We compare the numerically derived model with previously obtained analytical results. In addition to the usual hopping terms between oxygens tpp and Cu-Cu exchange terms Jdd, the model also includes a strong copper-oxygen exchange interaction Jpd and a Kondo-like spin-flip oxygen-oxygen hopping term Kpdp. We use the density matrix renormalization group to study the charge, spin, and pairing properties of the derived model on ladder systems.

Constitutive Behavior and Modeling of Al-Cu Alloy Systems

DTIC Science & Technology

2013-05-01

Mechanical Threshold of Dynamically Deformed Copper and Nitronic 40 ." Journal de Physique, 1985: 25- 34. Gama, B. A., S. L. Lopatnikov, and J. W. G...38 3. MODIFIED ZERILLI-ARMSTRONG MODEL .................................... 40 3.1 Introduction... 40 3.2 Former Modifications to ZA Model by Zerilli and Armstrong .. 42 3.3 Modifications to ZA Model

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

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Modification of surface layers of copper under the action of the volumetric discharge initiated by an avalanche electron beam in nitrogen and CO2 at atmospheric pressure

NASA Astrophysics Data System (ADS)

Shulepov, M. A.; Akhmadeev, Yu. Kh.; Tarasenko, V. F.; Kolubaeva, Yu. A.; Krysina, O. V.; Kostyrya, I. D.

2011-05-01

The results of experimental investigations of the action of the volumetric discharge initiated by an avalanche electron beam on the surface of copper specimens are presented. The volumetric (diffuse) discharge in nitrogen and CO2 at atmospheric pressure was initiated by applying high voltage pulses of nanosecond duration to a tubular foil cathode. It has been found that the treatment of a copper surface by this type of discharge increases the hardness of the surface layer due to oxidation.

Copper-doped waveguides in glass substrates

NASA Astrophysics Data System (ADS)

Spirkova-Hradilova, Jarmila; Tresnakova-Nebolova, Pavlina; Jirka, Ivan; Mach, Karel; Perina, Vratislav; Mackova, Anna; Kuncova, Gabriela

2001-05-01

We have studied fabrication and properties of copper ion- exchanged waveguides fabricated in various types of special soda-lime silicate glass as well as commercial optical glass substrates. The ion exchange was performed in melts containing either CuI or CuII at temperatures from 350 degrees C to 500 degrees C for times ranging from 5 minutes to 21 hrs. Optical properties of the fabricated waveguides were studied using mode spectroscopy and photoluminescence spectroscopy and composition of the waveguides was determined by SEM, RBS, EPR and ESCA. After the ion exchange the refractive index increased, according to fabrication conditions, up to (Delta) n equals +0.0693 and the guides supported up to 16 TE and TM modes. The CuI $ARLR CuII redox reaction during the fabrication depended strongly on the composition as well as the temperature of the reaction melts. In the Cu2Cl2ZnCl2 melts the oxidation of CuI to CuII was strongly hampered, so that CuI prevailed in the waveguiding region. These samples exhibited the most intensive blue-green luminescence, in spite of those fabricated using the CuII-based reaction melts, where practically no blue-green luminescence was observed. ESCA measurement revealed an easy charge transfer between the both oxidation states of copper in the very surface regions of the samples.

Composite Pulse Tube

NASA Technical Reports Server (NTRS)

Martin, Jerry L.; Cloyd, Jason H.

2007-01-01

A modification of the design of the pulse tube in a pulse-tube cryocooler reduces axial thermal conductance while preserving radial thermal conductance. It is desirable to minimize axial thermal conductance in the pulse-tube wall to minimize leakage of heat between the warm and cold ends of the pulse tube. At the same time, it is desirable to maximize radial thermal conductance at the cold end of the pulse tube to ensure adequate thermal contact between (1) a heat exchanger in the form of a stack of copper screens inside the pulse tube at the cold end and (2) the remainder of the cold tip, which is the object to which the heat load is applied and from which heat must be removed. The modified design yields a low-heat-leak pulse tube that can be easily integrated with a cold tip. A typical pulse tube of prior design is either a thin-walled metal tube or a metal tube with a nonmetallic lining. It is desirable that the outer surface of a pulse tube be cylindrical (in contradistinction to tapered) to simplify the design of a regenerator that is also part of the cryocooler. Under some conditions, it is desirable to taper the inner surface of the pulse tube to reduce acoustic streaming. The combination of a cylindrical outer surface and a tapered inner surface can lead to unacceptably large axial conduction if the pulse tube is made entirely of metal. Making the pulse-tube wall of a nonmetallic, lowthermal- conductivity material would not solve the problem because the wall would not afford the needed thermal contact for the stack of screens in the cold end. The modified design calls for fabricating the pulse tube in two parts: a longer, nonmetallic part that is tapered on the inside and cylindrical on the outside and a shorter, metallic part that is cylindrical on both the inside and the outside. The nonmetallic part can be made from G-10 fiberglass-reinforced epoxy or other low-thermal-conductivity, cryogenically compatible material. The metallic part must have high thermal conductivity in the cryogenic temperature range and would typically be made of pure copper to satisfy this requirement. The metallic part is bonded to the nonmetallic part with epoxy. Copper screens are inserted in the metallic part to form the cold-end heat exchanger, then the assembled pulse tube is inserted in the cold tip.

Ion Exchange Formation via Sulfonated Bicomponent Nonwovens

NASA Astrophysics Data System (ADS)

Stoughton, Hannah L.

For many years ion exchange resins were used to: remove heavy metals from water, recover materials from wastewater, and eliminate harmful gases from the air. While use of these resin beads dominates the ion exchange industry, the beads have limitations that should be considered when decisions are made to employ them. For instance, officials must balance the inherent zero sum surface area and porosity of the materials. This series of studies investigates the use of bicomponent nonwovens as a base substrate for producing high surface area ion exchange materials for the removal of heavy metal ions. Functionalized materials were produced in a two-step process: (1) PET/PE spunbond bicomponent fibers were fractured completely, producing the high surface area nonwoven to be used as the base ion exchange material, and (2) the conditions for functionalizing the PET fibers of the nonwoven webs were investigated where an epoxy containing monomer was grafted to the surface followed by sulfonation of the monomer. The functionalization reactions of the PET fibers were monitored based on: weight gain, FTIR, TOF-SIMS, and SEM. Ion exchange properties were evaluated using titration and copper ion removal capacity from test solutions. The relationship between web structure and removal efficiency of the metal ions was defined through a comparison of the bicomponent and homocomponent nonwovens for copper ion removal efficiency. The investigation revealed that utilizing the high surface area, fractured bicomponent nonwoven ion exchange materials with capacities comparable to commercially available ion exchange resins could be produced.

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

DOE PAGES

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu; ...

2017-09-21

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

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

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

Copper retention, calcium release and ultrastructural evidence indicate specific Cuprolinic Blue uptake and peculiar modifications in mineralizing aortic valves.

PubMed

Ortolani, F; Tubaro, F; Petrelli, L; Gandaglia, A; Spina, M; Marchini, M

2002-01-01

Previously, reactions with copper phthalocyanines at 0.05 M critical electrolyte concentration were found to cause demineralization in calcifying porcine aortic valves after subdermal implantation in rat, as well as simultaneous visualization of peculiar phthalocyanine-positive layers around cells and cell-derived matrix vesicles. In the present investigation, an appraisal was made of the mechanism and specificity of reactions with Cuprolinic Blue by comparing quantitatively calcium release and copper retention by calcified aortic valves reacted with this phthalocyanine under different critical electrolyte concentration conditions, and the corresponding ultrastructural patterns. It was found that (i) decalcifying properties are inversely proportional to salt molarity; (ii) reactivity to Cuprolinic Blue is critical electrolyte concentration-dependent, since the greatest copper retention occurred in 0.05 M critical electrolyte concentration Cuprolinic Blue-reacted samples, the only ones that also exhibited phthalocyanine-positive layers; (iii) the appearance of phthalocyanine-positive layers depends on Cuprolinic Blue uptake, revealing pericellular clustering of calcium-binding, anionic molecules; and (iv) minor Cuprolinic Blue uptake occurs by residual proteoglycans which still remain in the extracellular matrix after 6-week-long subdermal implantation. The present results indicate that this method is appropriate for the study of mineralized tissues and illustrate peculiar tissue modifications occurring at least in the experimental conditions used here.

Sulfonato-imino copper(ii) complexes: fast and general Chan-Evans-Lam coupling of amines and anilines.

PubMed

Hardouin Duparc, V; Schaper, F

2017-10-14

Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.

Regulating the Regulator: Post-Translational Modification of Ras

PubMed Central

Ahearn, Ian M.; Haigis, Kevin; Bar-Sagi, Dafna; Philips, Mark R.

2013-01-01

Ras proteins are monomeric GTPases that act as binary molecular switches to regulate a wide range of cellular processes. The exchange of GTP for GDP on Ras is regulated by guanine nucleotide exchange factors (GEFs) and GTPase activating proteins (GAPs), which regulate the activation state of Ras without covalently modifying it. In contrast, post-translational modifications (PTMs) of Ras proteins direct them to various cellular membranes and, in some cases, modulate GTP–GDP exchange. Important Ras PTMs include the constitutive and irreversible remodelling of its C-terminal CAAX motif by farnesylation, proteolysis and methylation, reversible palmitoylation, and conditional modifications including phosphorylation, peptidyl-proly isomerisation, mono- and di-ubiquitination, nitrosylation, ADP ribosylation and glucosylation. PMID:22189424

Stormwater filtration of toxic heavy metal ions using lignocellulosic materials selection process, fiberization, chemical modification, and mat formation

Treesearch

James S. Han

1999-01-01

Lignocellulosic materials were evaluated for their effectiveness in filtering toxic heavy metals from stormwater. Kenaf, alfalfa, juniper, and aspen fibers were used as models to evaluate the effectiveness and limitations of chemical modification and the extent of fiber degradation. Individual and mixed aqueous solutions of nickel, copper, zinc, and cadmium in various...

[Transformation of Cu forms in Cynodon dactylon rhizosphere soil of copper tailings yard].

PubMed

Wang, You-bao; Huang, Yong-jie; Zhen, Quan; Yan, Mi; Yang, Hong-fei; Liu, Deng-yi

2007-06-01

The study on the Cu forms in Cynodon dactylon rhizosphere soil of copper tailings yard in Tongling City, Anhui Province showed that among the test Cu forms, the amount of residual form occupied the majority, while that of exchangeable form was relatively low. Compared with non-rhizosphere soil, rhizosphere soil had a higher organic matter content but a lower pH. With the growth of C. dactylon, the contents of organically combined and exchangeable Cu in rhizosphere soil increased by 7.89% and 5%, respectively, while those of carbonate-combined and Fe-Mn oxides-combined Cu decreased. The growth of C. dactylon accelerated the transformation of Cu forms in rhizosphere soil, and decreased the rhizosphere soil Cu content through its absorption.

Synthesis of polymer ion-exchange hydrogels under γ - irradiation 60Co

NASA Astrophysics Data System (ADS)

Le, V. M.; Zhevnyak, V. D.; Pak, V. Kh; Ananev, V. A.; Borodin, U. V.

2015-04-01

We have reported earlier about the modification of ion-exchange hydrogel under the influence of gamma radiation. The optimal absorbed dose of irradiation had been choosen for radiation modification of polymer hydrogels by ionits to produce products with a high content of the gel - fractions and sufficient mechanical properties. The dependence of the static exchange capacity of hydrogels on the type of ionit and its fractional composition had been studied. The dependence of the static exchange capacity of the quantitative composition of the ionit in the volume of the hydrogel had been investigated. The ion-exchange medical eye lenses had been made under selected conditions of synthesis. Their sorption properties had been studied.

Surface functionalization of copper via oxidative graft polymerization of 2,2'-bithiophene and immobilization of silver nanoparticles for combating biocorrosion.

PubMed

Wan, Dong; Yuan, Shaojun; Neoh, K G; Kang, E T

2010-06-01

An environmentally benign approach to surface modification was developed to impart copper surface with enhanced resistance to corrosion, bacterial adhesion and biocorrosion. Oxidative graft polymerization of 2,2'-bithiophene from the copper surface with self-assembled 2,2'-bithiophene monolayer, and subsequent reduction of silver ions to silver nanoparticles (Ag NPs) on the surface, give rise to a homogeneous bithiophene polymer (PBT) film with densely coupled Ag NPs on the copper surface (Cu-g-PBT-Ag NP surface). The immobilized Ag NPs were found to significantly inhibit bacterial adhesion and enhance the antibacterial properties of the PBT modified copper surface. The corrosion inhibition performance of the functionalized copper substrates was evaluated by Tafel polarization curves and electrochemical impedance spectroscopy. Arising from the chemical affinity of thiols for the noble and coinage metals, the copper surface functionalized with both PBT brushes and Ag NPs also exhibits long-term stability, and is thus potentially useful for combating the combined problems of corrosion and biocorrosion in harsh marine and aquatic environments.

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

Chumakov, Yu. M.; Paholnitcaia, A. Yu.; Petrenko, P. A.

Two crystal modifications of nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper (I and II) and two modifications of chloro-(2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) copper (III and IV) have been synthesized and studied by X-ray diffraction. In structures I and II, the copper atoms coordinate a monodeprotonated molecule of the organic ligand, nitrate ions, and a water molecule. In crystals of I, the complexes are monomeric, whereas complexes II are linked via nitrate ions to form polymeric chains. In both structures the coordination polyhedron of the copper atom can be described as a distorted tetragonal bipyramid—(4 + 1 + 1) in I and (4 + 2) in II. These coordinationmore » polyherdra have different compositions. In structures III and IV, the metal atoms coordinate a monodeprotonated (2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazole molecule and chloride ions. In III the complex-forming ion has square-planar coordination geometry, whereas structure IV consists of centrosymmetric dimers with two bridging chlorine atoms. It was found that nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper possesses antitumor activity.« less

Method of producing .sup.67 Cu

DOEpatents

O'Brien, Jr., Harold A.; Barnes, John W.; Taylor, Wayne A.; Thomas, Kenneth E.; Bentley, Glenn E.

1984-01-01

A method of producing carrier-free .sup.67 Cu by proton spallation combined with subsequent chemical separation and purification is disclosed. A target consisting essentially of pressed zinc oxide is irradiated with a high energy, high current proton beam to produce a variety of spallogenic nuclides, including .sup.67 Cu and other copper isotopes. The irradiated target is dissolved in a concentrated acid solution to which a palladium salt is added. In accordance with the preferred method, the spallogenic copper is twice coprecipitated with palladium, once with metallic zinc as the precipitating agent and once with hydrogen sulfide as the precipitating agent. The palladium/copper precipitate is then dissolved in an acid solution and the copper is separated from the palladium by liquid chromatography on an anion exchange resin.

Method for producing /sup 67/Cu

DOEpatents

O'Brien, H.A. Jr.; Barnes, J.W.; Taylor, W.A.; Thomas, K.E.; Bentley, G.E.

A method of producing carrier-free /sup 67/Cu by proton spallation combined with subsequent chemical separation and purification is disclosed. A target consisting essentially of pressed zinc oxide is irradiated with a high energy, high current proton beam to produce a variety of spallogenic nuclides, including /sup 67/Cu and other copper isotopes. The irradiated target is dissolved in a concentrated acid solution to which a palladium salt is added. In accordance with the preferred method, the spallogenic copper is twice coprecipitated with palladium, once with metallic zinc as the precipitating agent and once with hydrogen sulfide as the precipitating agent. The palladium/copper precipitate is then dissolved in an acid solution and the copper is separated from the palladium by liquid chromatography on an anion exchange resin.

Synthesis of single-site copper catalysts for methane partial oxidation

DOE PAGES

Grundner, S.; Luo, W.; Sanchez-Sanchez, M.; ...

2015-12-24

Cu-Exchanged zeolites are known as active materials for methane oxidation to methanol. However, understanding of the formation of Cu active species during synthesis, dehydration and activation is fragmented and rudimentary. We show here how a synthesis protocol guided by insight in the ion exchange elementary steps leads to highly uniform Cu species in mordenite (MOR).

Designing multistep transformations using the Hammett equation: imine exchange on a copper(I) template.

PubMed

Schultz, David; Nitschke, Jonathan R

2006-08-02

Herein, we quantify how imine exchange may be used to selectively transform one metallo-organic structure into another. A series of imine exchange reactions were studied, involving a set of 4-substituted anilines, their 2-pyridylimines and 1,10-phenanthrolyl-2,9-diimines, as well as the copper complexes of these imine ligands. Electron-rich anilines were found to displace electron-poor anilines in all cases. Linear free energy relationships (LFERs) were discovered connecting the electron-donating or -withdrawing character of the 4-substituent of an aniline, as measured by the Hammett sigma(para) parameter, to that aniline's ability to compete with unsubstituted aniline to form imines. The quality of these LFERs allowed for quantitative predictions: to obtain the desired degree of selectivity in an imine exchange between anilines A and B, the required sigma(para) differential could be predicted using a variant of the Hammett equation, log(K(AB)) = rho(sigma(A) - sigma(B)). We validated this methodology by designing and executing a three-step transformation of a series of copper(I)-containing structures. Each step proceeded in predictably high yield, as calculated from sigma differentials. At each step in the series of transformations, macrocyclic structures could be created or destroyed through the selection of mono- or di-amines as subcomponents. The same methodology could be used to predict the formation of a diverse dynamic library of helicates from a set of four aniline precursors, as well as the collapse of this library into one helicate upon the addition of a fifth aniline.

Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

PubMed

Kasumov, Veli T; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

2013-03-01

New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μ(B) per Cu(II)) and 6 (2.79 μ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

An evaluation of a hybrid ion exchange electrodialysis process in the recovery of heavy metals from simulated dilute industrial wastewater.

PubMed

Mahmoud, Akrama; Hoadley, Andrew F A

2012-06-15

Hybrid ion exchange electrodialysis, also called electrodeionization (IXED), is a technology in which a conventional ion exchange (IX) is combined with electrodialysis (ED) to intensify mass transfer and to increase the limiting current density and therefore to carry out the treatment process more effectively. It allows the purification of metal-containing waters, as well as the production of concentrated metal salt solutions, which could be recycled. The objective of this paper was to investigate the ability of the IXED technique for the treatment of acidified copper sulphate solutions simulating rinsing water of copper plating lines. A single-stage IXED process at lab-scale with a small bed of ion exchanger resin with a uniform composition was evaluated, and the treatment performance of the process was thoroughly investigated. The IXED stack was assembled as a bed layered with the ion exchanger resin (strong acid cation-exchange Dowex™) and inert materials. The stack configuration was designed to prevent a non-uniform distribution of the current in the bed and to allow faster establishment of steady-state in the cell for IXED operation. The influence of operating conditions (e.g. ion exchanger resin with a cross-linking degree from 2 to 8% DVB, and current density) on IXED performance was examined. A response surface methodology (RSM) was used to evaluate the effects of the processing parameters of IXED on (i) the abatement yield of the metal cation, which is a fundamental purification parameter and an excellent indicator of the extent of IXED, (ii) the current yield or the efficiency of copper transport induced by the electrical field and (iii) the energy consumption. The experimental results showed that the performance at steady-state of the IXED operation with a layered bed remained modest, because of the small dimension of the bed and notably the current efficiency varied from 25 to 47% depending on the conditions applied. The feasibility of using the IXED in operations for removal of heavy metals from moderately dilute rinsing waters was successfully demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Organic Complexation of Dissolved Copper and Iron from Shipboard Incubations in the Central California Current System: Investigating the Impacts of Light Conditions and Phytoplankton Growth on Iron- and Copper-Binding Ligand Characteristics

NASA Astrophysics Data System (ADS)

Mellett, T.; Parker, C.; Brown, M.; Coale, T.; Duckham, C.; Chappell, D.; Maldonado, M. T.; Bruland, K. W.; Buck, K. N.

2016-02-01

Two shipboard incubation experiments were carried out in July of 2014 to investigate potential sources and sinks of iron- and copper-binding organic ligands in the surface ocean. Seawater for the experiments was collected from the central California Current System (cCCS) and incubated under varying light conditions and in the presence and absence of natural phytoplankton communities. Incubation treatments were sampled over a period of up to 3 days for measurements of total dissolved copper and iron, and for the concentration and conditional stability constants of copper- and iron-binding organic ligands. Dissolved copper and iron were determined by inductively coupled plasma-mass spectrometry (ICP-MS) following preconcentration on a Nobias PA1 resin. Organic ligand characteristics for iron and copper were determined using a method of competitive ligand exchange-absorptive cathodic stripping voltammetry (CLE-ACSV) with the added competing ligand salicylaldoxime. Trends in ligand concentrations and conditional stability constants across the different treatments and over the course of the incubation experiments will be presented.

Improved Electroformed Structural Copper and Copper Alloys

NASA Technical Reports Server (NTRS)

Malone, G. A.; Hudson, W.; Babcock, B.; Edwards, R.

1998-01-01

Electroforming offers a superior means for fabricating internally cooled heat exchangers and structures subjected to thermal environments. Copper is deposited from many such applications because of the good thermal conductivity. It suffers from mediocre yield strength as a structural material and loses mechanical strength at intermediate temperatures. Mechanical properties similar to those of electroformed nickel are desired. Phase 1 examined innovative means to improve deposited copper structural performance. Yield strengths as high as 483 MPa (70 ksi) were obtained with useful ductility while retaining a high level of purity essential to good thermal conductivity. Phase 2 represents a program to explore new additive combinations in copper electrolytes to produce a more fine, equiaxed grain which can be thermally stabilized by other techniques such as alloying in modest degrees and dispersion strengthening. Evaluation of new technology - such as the codeposition of fullerness (diamond-like) particles were made to enhance thermal conductivity in low alloys. A test fire quality tube-bundle engine was fabricated using these copper property improvement concepts to show the superiority of the new coppers and fabrications methods over competitive technologies such as brazing and plasma deposition.

Removal of phosphate using copper-loaded polymeric ligand exchanger prepared by radiation grafting of polypropylene/polyethylene (PP/PE) nonwoven fabric

NASA Astrophysics Data System (ADS)

Barsbay, Murat; Kavaklı, Pınar Akkaş; Güven, Olgun

2010-03-01

A novel polymeric ligand exchanger (PLE) was prepared for the removal of phosphate ions from water. 2,2'-dipyridylamine (DPA), a bidentate ligand forming compound with high coordination capacity with a variety of metal ions was bound to glycidyl methacrylate (GMA) grafted polypropylene/polyethylene (PP/PE) nonwoven fabric synthesized by radiation-induced grafting technique. DPA attachment on epoxy ring of GMA units was tested in different solvents, i.e. methanol, ethanol, dioxane and dimethylsulfoxide (DMSO). The highest amount of modification was achieved in dioxane. In order to prepare the corresponding PLE for the removal of phosphate, DPA-immobilized fabric was loaded with Cu(II) ions. Phosphate adsorption experiments were performed in batch mode at different pH (5-9) and phosphate concentrations. The fabric was found to be effective for the removal of phosphate ions. At every stage of preparation and use, the nonwoven fabric was characterized by thermal (i.e. DSC and TGA) and spectroscopic (FTIR) methods. Competitive adsorption experiments were also carried out using two solutions with different concentration levels at pH 7 to see the effect of competing ions. Phosphate adsorption was found to be effective and selective from solutions having trace amounts of competitive anions. It is expected that the novel PLE synthesized can be used for the removal of phosphate ions in low concentrations over a large range of pH.

Human cytoplasmic copper chaperones Atox1 and CCS exchange copper ions in vitro.

PubMed

Petzoldt, Svenja; Kahra, Dana; Kovermann, Michael; Dingeldein, Artur P G; Niemiec, Moritz S; Ådén, Jörgen; Wittung-Stafshede, Pernilla

2015-06-01

After Ctr1-mediated copper ion (Cu) entry into the human cytoplasm, chaperones Atox1 and CCS deliver Cu to P1B-type ATPases and to superoxide dismutase, respectively, via direct protein-protein interactions. Although the two Cu chaperones are presumed to work along independent pathways, we here assessed cross-reactivity between Atox1 and the first domain of CCS (CCS1) using biochemical and biophysical methods in vitro. By NMR we show that CCS1 is monomeric although it elutes differently from Atox1 in size exclusion chromatography (SEC). This property allows separation of Atox1 and CCS1 by SEC and, combined with the 254/280 nm ratio as an indicator of Cu loading, we demonstrate that Cu can be transferred from one protein to the other. Cu exchange also occurs with full-length CCS and, as expected, the interaction involves the metal binding sites since mutation of Cu-binding cysteine in Atox1 eliminates Cu transfer from CCS1. Cross-reactivity between CCS and Atox1 may aid in regulation of Cu distribution in the cytoplasm.

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

Jin, Xin; Zhou, Pei; Zheng, Chunying

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

Controlled synthesis of carbon-encapsulated copper nanostructures by using smectite clays as nanotemplates.

PubMed

Tsoufis, Theodoros; Colomer, Jean-François; Maccallini, Enrico; Jankovič, Lubos; Rudolf, Petra; Gournis, Dimitrios

2012-07-23

Rhomboidal and spherical metallic-copper nanostructures were encapsulated within well-formed graphitic shells by using a simple chemical method that involved the catalytic decomposition of acetylene over a copper catalyst that was supported on different smectite clays surfaces by ion-exchange. These metallic-copper nanostructures could be separated from the inorganic support and remained stable for months. The choice of the clay support influenced both the shape and the size of the synthesized Cu nanostructures. The synthesized materials and the supported catalysts from which they were produced were studied in detail by TEM and SEM, powder X-ray diffraction, thermal analysis, as well as by Raman and X-ray photoelectron spectroscopy. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Copper (II) Containing Phosphomolybdic Acid Salt as Catalyst for the Synthesis of Biodiesel by Esterification.

PubMed

Cai, Jie; Zhang, Qiu-Yun; Wei, Fang-Fang; Huang, Jin-Shu; Feng, Yun-Mei; Ma, Hai-Tao; Zhang, Yutao-

2018-04-01

Copper (II) containing phosphomolybdic acid (PMA) catalysts were synthesized by ion exchange method and characterization using various physico-chemical techniques such as X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), thermogravimetric (TG) and scanning electron microscopy (SEM). The characterization results showed that the Keggin ions were retained in the catalysts and possessed well thermal stability. The catalytic esterification of lauric acid with methanol could be easily achieved about 78.7% conversion under optimum condition, the catalyst also contributed to the stability of the catalyst in which it can be reused for a certain time. This study demonstrated an alternative approach to biodiesel production with high efficiency by Cu (II) ion exchanged phosphomolybdic acid catalyst in the esterification catalytic.

Electrochemical evidences and consequences of significant differences in ions diffusion rate in polyacrylate-based ion-selective membranes.

PubMed

Woźnica, Emilia; Mieczkowski, Józef; Michalska, Agata

2011-11-21

The origin and effect of surface accumulation of primary ions within the ion-selective poly(n-butyl acrylate)-based membrane, obtained by thermal polymerization, is discussed. Using a new method, based on the relation between the shape of a potentiometric plot and preconditioning time, the diffusion of copper ions in the membrane was found to be slow (the diffusion coefficient estimated to be close to 10(-11) cm(2) s(-1)), especially when compared to ion-exchanger counter ions--sodium cations diffusion (a diffusion coefficient above 10(-9) cm(2) s(-1)). The higher mobility of sodium ions than those of the copper-ionophore complex results in exposed ion-exchanger role leading to undesirably exposed sensitivity to sodium or potassium ions.

Preparation of tritium-labeled optical isomers of amino acids by ligand exchange chromatography on polyacrylamide sorbent containing L-phenylalanine groupings

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

Zolotarev, Yu.A.; Penkina, V.I.; Dostavalov, I.N.

Tritium-labeled optically active amino acids are obtained by resolving racemates of the corresponding amino acids by chromatography on a chiral polyacrylamide sorbent, filled with copper ions. The chiral sorbent is obtained by the action of formaldehyde and L-phenylalanine on a Biogel P-4 polyacrylamide gel in an alkaline medium. Data are given on the ligand exchange chromatography of amino acids on this sorbent, depending on the degree of filling of the sorbent by copper ions and the concentration of the eluent. Conditions were selected for the quantitative resolution of racemates of amino acids and examples are given of a preparative obtainingmore » of tritium labeled optical isomers of amino acids.« less

In Situ Synthesis of Lipid Membranes

NASA Astrophysics Data System (ADS)

Devaraj, N. K.

2017-07-01

We have a strong interest in applying covalent coupling reactions to the formation and modification of lipid membranes. We have utilized chemoselective reactions, such as copper-catalyzed triazole formation or the native chemical ligation.

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

PubMed

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

2017-12-01

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

Casting Characteristics of High Cerium Content Aluminum Alloys

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

Weiss, D; Rios, O R; Sims, Z C

This paper compares the castability of the near eutectic aluminum-cerium alloy system to the aluminum-silicon and aluminum-copper systems. The alloys are compared based on die filling capability, feeding characteristics and tendency to hot tear in both sand cast and permanent mold applications. The castability ranking of the binary Al–Ce systems is as good as the aluminum-silicon system with some deterioration as additional alloying elements are added. In alloy systems that use cerium in combination with common aluminum alloying elements such as silicon, magnesium and/or copper, the casting characteristics are generally better than the aluminum-copper system. In general, production systems formore » melting, de-gassing and other processing of aluminum-silicon or aluminum-copper alloys can be used without modification for conventional casting of aluminum-cerium alloys.« less

Physiological serum copper concentrations found in malignancies cause unfolding induced aggregation of human serum albumin in vitro.

PubMed

Rizvi, Asim; Furkan, Mohd; Naseem, Imrana

2017-12-15

Malignancies are characterized by several drastic metabolic changes, one of which is a progressive rise in the levels of serum copper. This rise in serum copper is documented across all malignancies and across malignancies in several species. This study aims to explore in vitro the effect of increased copper levels on the structure of the blood protein human serum albumin. Exposure of human serum albumin to physiologically relevant copper concentrations for 21 days resulted in structural modifications in the protein which were evident by changes in the intrinsic florescence. A loss of the predominantly alpha helical structure of human serum albumin was recorded along with a tendency to form protein aggregates. This aggregation was characterized by Thioflavin T and Congo Red assays. Rayleigh light scattering and turbidity assays confirmed aggregation. The aggregates were visually confirmed using transmission electron microscopy. This is the first report implicating increased copper levels as a cause of aggregation of blood proteins in malignancies. The physiological and biochemical implications of this phenomenon are discussed. Copyright © 2017. Published by Elsevier Inc.

Surface modification of malachite with ethanediamine and its effect on sulfidization flotation

NASA Astrophysics Data System (ADS)

Feng, Qicheng; Zhao, Wenjuan; Wen, Shuming

2018-04-01

Ethanediamine was used to modify the mineral surface of malachite to improve its sulfidization and flotation behavior. The activation mechanism was investigated by adsorption experiments, X-ray photoelectron spectroscopy (XPS) analysis, and zeta potential measurements. Microflotation experiments showed that the flotation recovery of malachite was enhanced after the pretreatment of the mineral particles with ethanediamine prior to the addition of Na2S. Adsorption tests revealed that numerous sulfide ion species in the pulp solution were transferred onto the mineral surface through the formation of more copper sulfide species. This finding was confirmed by the results of the XPS measurements. Ethanediamine modification not only increased the contents of copper sulfide species on the malachite surface but also enhanced the reactivity of the sulfidization products. During sulfidization, Cu(II) species on the mineral surface were reduced into Cu(I) species, and the percentages of S22- and Sn2- relative to the total S increased after modification, resulting in increased surface hydrophobicity. The results of zeta potential measurements showed that the ethanediamine-modified mineral surface adsorbed with more sulfide ion species was advantageous to the attachment of xanthate species, thereby improving malachite floatability. The proposed ethanediamine modification followed by sulfidization xanthate flotation exhibits potential for industrial application.

Application of diffuse discharges of atmospheric pressure formed by runaway electrons for modification of copper and stainless steel surface

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

Tarasenko, V. F., E-mail: VFT@loi.hcei.tsc.ru; Shulepov, M. A.; Erofeev, M. V.

The results of studies devoted to the influence of a runaway electron pre-ionized diffuse discharge (REP DD) formed in air and nitrogen at atmospheric pressure on the surface of copper and stainless steel are presented. Nanosecond high-voltage pulses were used to obtain REP DD in different gases at high pressures in a chamber with a flat anode and a cathode possessing a small radius of curvature. This mode of discharge was implemented owing to the generation of runaway electrons and X-rays. The conditions under which the surface of copper and stainless steel was cleaned from carbon and oxidized are described.

Effects of etchants in the transfer of chemical vapor deposited graphene

NASA Astrophysics Data System (ADS)

Wang, M.; Yang, E. H.; Vajtai, R.; Kono, J.; Ajayan, P. M.

2018-05-01

The quality of graphene can be strongly modified during the transfer process following chemical vapor deposition (CVD) growth. Here, we transferred CVD-grown graphene from a copper foil to a SiO2/Si substrate using wet etching with four different etchants: HNO3, FeCl3, (NH4)2S2O8, and a commercial copper etchant. We then compared the quality of graphene after the transfer process in terms of surface modifications, pollutions (residues and contaminations), and electrical properties (mobility and density). Our tests and analyses showed that the commercial copper etchant provides the best structural integrity, the least amount of residues, and the smallest doping carrier concentration.

Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

PubMed

Klimovica, Kristine; Kirschbaum, Kristin; Daugulis, Olafs

2016-09-12

Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a . The upper limit of Δ G ‡ , assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Δ G 298 ‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9 , with Δ G 298 ‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

78 FR 26669 - Self-Regulatory Organizations; EDGX Exchange, Inc.; Notice of Filing and Immediate Effectiveness...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-07

... gigabyte Copper circuit; $750 per physical port that connects to the System via a 1 gigabyte Fiber circuit; and $1,000 per physical port that connects to the System via a 10 gigabyte Fiber circuit. The Exchange... physical port that connects to the System via a 1 gigabyte Fiber circuit from $750 to $1,000; (ii) increase...

The delivery of copper for thylakoid import observed by NMR

PubMed Central

Banci, Lucia; Bertini, Ivano; Ciofi-Baffoni, Simone; Kandias, Nikolaos G.; Robinson, Nigel J.; Spyroulias, Georgios A.; Su, Xun-Cheng; Tottey, Stephen; Vanarotti, Murugendra

2006-01-01

The thylakoid compartments of plant chloroplasts are a vital destination for copper. Copper is needed to form holo-plastocyanin, which must shuttle electrons between photosystems to convert light into biologically useful chemical energy. Copper can bind tightly to proteins, so it has been hypothesized that copper partitions onto ligand-exchange pathways to reach intracellular locations without inflicting damage en route. The copper metallochaperone Atx1 of chloroplast-related cyanobacteria (ScAtx1) engages in bacterial two-hybrid interactions with N-terminal domains of copper-transporting ATPases CtaA (cell import) and PacS (thylakoid import). Here we visualize copper delivery. The N-terminal domain PacSN has a ferredoxin-like fold that forms copper-dependent heterodimers with ScAtx1. Removal of copper, by the addition of the cuprous-ion chelator bathocuproine disulfonate, disrupts this heterodimer, as shown from a reduction of the overall tumbling rate of the protein mixture. The NMR spectral changes of the heterodimer versus the separate proteins reveal that loops 1, 3, and 5 (the carboxyl tail) of the ScAtx1 Cu(I) site switch to an apo-like configuration in the heterodimer. NMR data (2JNH couplings in the imidazole ring of 15N ScAtx1 His-61) also show that His-61, bound to copper(I) in [Cu(I)ScAtx1]2, is not coordinated to copper in the heterodimer. A model for the PacSN/Cu(I)/ScAtx1 complex is presented. Contact with PacSN induces change to the ScAtx1 copper-coordination sphere that drives copper release for thylakoid import. These data also elaborate on the mechanism to keep copper(I) out of the ZiaAN ATPase zinc sites. PMID:16707580

Condition of copper and organic matter in the soil contaminated with metal remediation of humic substances.

NASA Astrophysics Data System (ADS)

Kolchanova, Kseniia; Barsova, Natalia; Motuzova, Galina; Stepanov, Andrey; Karpukhin, Mikhail

2017-04-01

The aim of this study was to investigate the forms of copper and transformation of organic matter in the soil under the influence of humic substances (potassium humate, which was obtained from coal). The object of research was the top layer of soil model field experience. Field experiments were carried out in 10-liter plastic containers.The upper layers were constructed artificially as mixture of loam, sand and peat. Below it was a layer of loam, then gravel and under it we installed lysimeters. The experiment was conducted in 3 settings: 1) control, 2) control + Cu, and 3) control + Cu + potassium humate . Copper was deposited into upper layer at soil column construction as dry powder (CuSO4*5H2O), which is 1000mg per kg. Humic substance was introduced on surface as liquid form. The focus was the state of the copper and organic matter of solid and liquid phase. In the solid phase pH, carbon content, the molecular-mass distributions for the organic matter, total (HNO3 conc.+ H2O2; decomposition in a microwave oven) and acid-soluble (1H HNO3) copper content, sequential extraction of copper (1 M MgCl2, acetate buffer pH 4,8 (AAB), 1% EDTA) were determined. For liquid phase characteristics aqueous extract was obtained and identified therein: pH, total activity and copper content and water-soluble organic matter(WOM) amphiphilic properties. The introduction of copper is accompanied by a decrease in pH in soils from 7 to 6,3. The introduction of the humic substance softens this effect. Introducing humic preparation gives an increase in carbon at 0.5%. HS and copper has no significant effect on the molecular-mass distribution of solid organic matter. Only about 4% introduced copper accounted for the exchangeable form (MgCl2) for the variant only copper contaminated. Copper, mainly precipitated as hydroxides, moved in an AAB extract. And compared with the exchangeable forms its quantity increases by 10 times. Still more copper goes into an extract of EDTA, about half of the total. That is, the introduction of humic substances increases the amount of copper associated with organic matter in complexes with high stability constants. The total amount of copper of the results of extraction is 88-96% of the all total content. Water-soluble copper contains only 0.5% of the total. But the introduction of humic substances increases the amount of water-soluble copper is 3 times. This is due to the increase in the content of the WOM by 2.5-3 times, both due to the hydrophobic and hydrophilic factions of WOM. And this leads to a sharp reduction in the activity of copper in the liquid phase. Dual effect of introducing humic substances was obtained on the results of the work. On the one hand the introduction of humic substances contributes the immobilization of copper by increasing the fraction associated with organic matter in the solid phase. On the other hand the introduction of humic substances contributes the mobilization of copper in the liquid phase due to the increase of WOM.

Biosorption of copper by cyanobacterial bloom-derived biomass harvested from the eutrophic Lake Dianchi in China.

PubMed

Wang, Kan; Colica, Giovanni; De Philippis, Roberto; Liu, Yongding; Li, Dunhai

2010-10-01

Biomass of cyanobacterial bloom from Lake Dianchi was used as a biosorbent for copper removal from aqueous solution. The maximum capacity was found at conditions of pH 4, initial concentration of copper was 10 mg/l and initial dose of biomass was 1.0 g/l. HNO(3) demonstrated the highest desorption efficiency compared with HCl, EDTA, and citric acid. Physical adsorption was assumed not to be the dominant mechanism of biosorption as revealed by scanning electron microscopy and surface area measurement of the biomass. Infrared ray spectra analysis of the biomass suggested that ion-exchange is the principal mechanism for biosorption. Considering the advantages-low cost, easy to collect, and huge in quantity-the Microcystis bloom biomass could be used as a sorbent for copper and other heavy metals removal.

Determination of labile copper, cobalt, and chromium in textile mill wastewater

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

Crain, J.S.; Essling, A.M.; Kiely, J.T.

1997-01-01

Copper, chromium, and cobalt species present in filtered wastewater effluent were separated by cation exchange and reverse phase chromatography. Three sample fractions were obtained: one containing metal cations (i.e., trivalent Cr, divalent Cu, and divalent Co), one containing organic species (including metallized dyes), and one containing other unretained species. The metal content of each fraction was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The sum of the corrected data was compared to the metal content of a filtered effluent aliquot digested totally with fuming sulfuric acid. Other aliquots of the filtered effluent were spiked with the metals ofmore » interest and digested to confirm chemical yield and accuracy. Method detection limits were consistently below 20 {mu}g L{sup -1} for Cu, 30 {mu}g L{sup -1} for Co, and 10 {mu}g L{sup -1} for Cr. Spike recoveries for undifferentiated Cu and Cr were statistically indistinguishable from unity; although Co spike recoveries were slightly low ({approximately}95%), its chemical yield was 98%. Copper retention on the sodium sulfonate cation exchange resin was closely correlated with the [EDTA]/[Cu] ratio, suggesting that metals retained upon the cation exchange column were assignable to labile metal species; however, mass balances for all three elements, though reasonable ({approximately}90%), were significantly different from unity. Mechanical factors may have contributed to the material loss, but other data suggest that some metal species reacted irreversibly with the reverse phase column. 3 refs., 2 figs., 4 tabs.« less

Preparation and characterization of (St-DVB-MAA) ion exchange resins

NASA Astrophysics Data System (ADS)

Jiang, Shanquan; Sun, Xiangwei; Ling, Lixing; Wang, Shumin; Wu, Wufeng; Cheng, Shihong; Hu, Yue; Zhong, Chunyan

2017-08-01

In this paper, used polyvinyl alcohol as dispersing agent, Benzoyl peroxide as initiator of polymerization, Divinyl benzene as cross-linking agent, Styrene and 2-Methylpropenoic acid as monomer, ion exchange resin (copolymer of St-DVB-MAA)were prepared by suspension polymerization on 80°C. The structures, components and properties of the prepared composite micro gels were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA). The experiment of ion exchange was conducted by resin to deal with copper ions in the solution. The result showed that performance of the ion exchange capacity was excellent, which impacted by pH.

The use of fibrous ion exchangers in gold hydrometallurgy

NASA Astrophysics Data System (ADS)

Kautzmann, R. M.; Sampaio, C. H.; Cortina, J. L.; Soldatov, V.; Shunkevich, A.

2002-10-01

This article examines a family of ion-exchange fibers, FIBAN, containing primary and secondary amine groups. These ion exchangers have a fiber diameter of 20 40 Μm, high osmotic and mechanic stability, a high rate of adsorption and regeneration, and excellent dynamic characteristics as filtering media. Inparticular, this article discusses the use of FIBAN fibrous ion exchangers in the recovery of gold cyanide andbase-metal cyanides (copper and mercury) from mineral-leaching solutions. The influence of polymer structure and water content on their extraction ability is described, along with key parameters of gold hydrometallurgy such as extraction efficiency, selectivity, pH dependence, gold cyanide loading, kinetics, and stripping.

Brazing open cell reticulated copper foam to stainless steel tubing with vacuum furnace brazed gold/indium alloy plating

DOEpatents

Howard, Stanley R [Windsor, SC; Korinko, Paul S [Aiken, SC

2008-05-27

A method of fabricating a heat exchanger includes brush electroplating plated layers for a brazing alloy onto a stainless steel tube in thin layers, over a nickel strike having a 1.3 .mu.m thickness. The resultant Au-18 In composition may be applied as a first layer of indium, 1.47 .mu.m thick, and a second layer of gold, 2.54 .mu.m thick. The order of plating helps control brazing erosion. Excessive amounts of brazing material are avoided by controlling the electroplating process. The reticulated copper foam rings are interference fit to the stainless steel tube, and in contact with the plated layers. The copper foam rings, the plated layers for brazing alloy, and the stainless steel tube are heated and cooled in a vacuum furnace at controlled rates, forming a bond of the copper foam rings to the stainless steel tube that improves heat transfer between the tube and the copper foam.

The effects of soil liming and sewage sludge application on dynamics of copper fractions and total copper concentration.

PubMed

Malinowska, Elżbieta

2016-10-01

The paper deals with effects of liming and different doses of municipal sewage sludge (5, 10, and 15 % of soil mass) on copper speciation in soil. In all samples, pH was determined together with total copper concentration, which was measured with the ICP-AES method. Concentration of copper chemical fractions was determined using the seven-step procedure of Zeien and Brümmer. In the soil treated with the highest dose of sludge (15 %), there was, compared to the control, a twofold increase in the concentration of copper and a threefold increase in the concentration of nitrogen. Copper speciation analysis showed that in the municipal sewage sludge the easily soluble and exchangeable fractions (F1 and F2) constituted only a small share of copper with the highest amount of this metal in the organic (F4) and residual (F7) fractions. In the soil, at the beginning of the experiment, the highest share was in the organic fraction (F4), the residual fraction (F7) but also in the fraction where copper is bound to amorphous iron oxides (F5). After 420 days, at the end of the experiment, the highest amount of copper was mainly in the organic fraction (F4) and in the fraction with amorphous iron oxides (F5). Due to mineralization of organic matter in the sewage sludge, copper was released into the soil with the share of the residual fraction (F7) decreasing. In this fraction, there was much more copper in limed soil than in non-limed soil.

Biochemical characterization of P-type copper ATPases

PubMed Central

Inesi, Giuseppe; Pilankatta, Rajendra; Tadini-Buoninsegni, Francesco

2014-01-01

Copper ATPases, in analogy with other members of the P-ATPase superfamily, contain a catalytic headpiece including an aspartate residue reacting with ATP to form a phosphoenzyme intermediate, and transmembrane helices containing cation-binding sites [TMBS (transmembrane metal-binding sites)] for catalytic activation and cation translocation. Following phosphoenzyme formation by utilization of ATP, bound copper undergoes displacement from the TMBS to the lumenal membrane surface, with no H+ exchange. Although PII-type ATPases sustain active transport of alkali/alkali-earth ions (i.e. Na+, Ca2+) against electrochemical gradients across defined membranes, PIB-type ATPases transfer transition metal ions (i.e. Cu+) from delivery to acceptor proteins and, prominently in mammalian cells, undergo trafficking from/to various membrane compartments. A specific component of copper ATPases is the NMBD (N-terminal metal-binding domain), containing up to six copper-binding sites in mammalian (ATP7A and ATP7B) enzymes. Copper occupancy of NMBD sites and interaction with the ATPase headpiece are required for catalytic activation. Furthermore, in the presence of copper, the NMBD allows interaction with protein kinase D, yielding phosphorylation of serine residues, ATP7B trafficking and protection from proteasome degradation. A specific feature of ATP7A is glycosylation and stabilization on plasma membranes. Cisplatin, a platinum-containing anti-cancer drug, binds to copper sites of ATP7A and ATP7B, and undergoes vectorial displacement in analogy with copper. PMID:25242165

Theoretical and Experimental Study of Thermoacoustic Engines

DTIC Science & Technology

1991-12-31

possible. In particulbr, we have considered use of extruded ceramic monolithic catalyst supports (for example, the ceramic used in some automobile...approximation. Heat exchangers retaken r be of negligible thickness and thus not to affect near-standing wave phasing. The TAB (or snack ) of length d is assumed...Heat exchangers were parallel plates of copper and the TAE is a monolithic catalyst support extruded ceramic. 13 15 The two-microphone-technique

All-metal, compact heat exchanger for space cryocoolers

NASA Technical Reports Server (NTRS)

Swift, Walter L.; Valenzuela, Javier; Sixsmith, Herbert

1990-01-01

This report describes the development of a high performance, all metal compact heat exchanger. The device is designed for use in a reverse Brayton cryogenic cooler which provides five watts of refrigeration at 70 K. The heat exchanger consists of a stainless steel tube concentrically assembled within a second stainless steel tube. Approximately 300 pairs of slotted copper disks and matching annular slotted copper plates are positioned along the centerline axis of the concentric tubes. Each of the disks and plates has approximately 1200 precise slots machined by means of a special electric discharge process. Positioning of the disk and plate pairs is accomplished by means of dimples in the surface of the tubes. Mechanical and thermal connections between the tubes and plate/disk pairs are made by solder joints. The heat exchanger assembly is 9 cm in diameter by 50 cm in length and has a mass of 10 kg. The predicted thermal effectiveness is greater than 0.985 at design conditions. Pressure loss at design conditions is less than 5 kPa in both fluid passages. Tests were performed on a subassembly of plates integrally soldered to two end headers. The measured thermal effectiveness of the test article exceeded predicted levels. Pressure losses were negligibly higher than predictions.

Ligand effects on the ferro- to antiferromagnetic exchange ratio in bis(o-semiquinonato)copper(II).

PubMed

Ovcharenko, Victor I; Gorelik, Elena V; Fokin, Sergey V; Romanenko, Galina V; Ikorskii, Vladimir N; Krashilina, Anna V; Cherkasov, Vladimir K; Abakumov, Gleb A

2007-08-29

Heterospin complexes [Cu(SQ)2Py].C7H8, Cu(SQ)2DABCO, and [Cu(SQ)2NIT-mPy].C6H6, where Cu(SQ)2 is bis(3,6-di-tert-butyl-o-benzosemiquinonato)copper(II), DABCO is 1,4-diazabicyclo(2,2,2)octane, and NIT-mPy is the nitronyl nitroxide 2-(pyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl, have been synthesized. The molecules of these complexes have a specific combination of the intramolecular ferro- and antiferromagnetic exchange interactions between the odd electrons of Cu(II) and SQ ligands, characterized by large exchange coupling parameters |J| approximately 100-300 cm(-1). X-ray and magnetochemical studies of a series of mixed-ligand compounds revealed that an extra ligand (Py, NIT-mPy, or DABCO) coordinated to the metal atom produces a dramatic effect on the magnetic properties of the complex, changing the multiplicity of the ground state. Quantum chemical analysis of magnetostructural correlations showed that the energy of the antiferromagnetic exchange interaction between the odd electrons of the SQ ligands in the Cu(SQ)2 bischelate is extremely sensitive to both the nature of the extra ligand and structural distortions of the coordination unit, arising from extra ligand coordination.

A Compendium of Brazed Microstructures For Fission Power Systems Applications

NASA Technical Reports Server (NTRS)

Locci, Ivan E.; Bowman, Cheryl L.

2012-01-01

NASA has been supporting design studies and technology development for fission-based power systems that could provide power to an outpost on the Moon, Mars, or an asteroid. Technology development efforts have included fabrication and evaluation of components used in a Stirling engine power conversion system. This investigation is part of the development of several braze joints crucial for the heat exchanger transfer path from a hot-side heat exchanger to a Stirling engine heat acceptor. Dissimilar metal joints are required to impart both mechanical strength and thermal path integrity for a heater head of interest. Preliminary design work for the heat exchanger involved joints between low carbon stainless steel to Inconel 718, where the 316L stainless steel would contain flowing liquid metal NaK while Inconel 718, a stronger alloy, would be used as structural reinforcement. This paper addressed the long-term microstructural stability of various braze alloys used to join 316L stainless steel heater head to the high conductivity oxygen-free copper acceptor to ensure the endurance of the critical metallic components of this sophisticated heat exchanger. The bonding of the 316L stainless steel heater head material to a copper heat acceptor is required to increase the heat-transfer surface area in contact with flowing He, which is the Stirling engine working fluid.

Studies on human fetal lens crystallins under oxidative stress and protective effects of tea polyphenols.

PubMed

Xiang, H; Pan, S; Li, S

1998-09-01

To investigate the oxidative modification of water-soluble crystallins of human fetal lens with H2O2 and fourteen metal ions with or without EDTA. Tea-polyphenols (TP) was added to above solutions in order to testing their antioxidative abilities. The experiments were performed at 37 degrees C with final concentration of 2.5 mg/ml protein, 0.1 mM metal ions, 0.3 mM EDTA and 1.0 mM H2O2. Then the TP was added to the solution with CuSO4 and H2O2, after 5 or 24 hours, the crystallins were analysed with SDS-PAGE and IEF. There were marked oxidative modifications of lens protein in H2O2 and copper without EDTA. In SDS-PAGE patterns, we found an increase in those species above of bands higher than 30 kD and some diffuse bands from 30 to 17 kD after 5 hours. In IEF patterns, there were a general increase on acidity with loss of the more basic species. When the TP was added, there was not any difference with control group. The results indicate that exposure of water-soluble protein to H2O2 and copper leads to covalent crosslinking and cleavage of polypeptides. After 24 hours, the development of the oxidative modifications of crystallins continues, comparison with the catalytic strength, copper ions stronger than the iron ions. On other hand, this work reported that the anti-oxidative action of TP is strong.

Fabrication and applications of copper sulfide (CuS) nanostructures

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

Shamraiz, Umair, E-mail: umairshamraiz@gmail.com; Hussain, Raja Azadar, E-mail: hussainazadar@gamil.com; Badshah, Amin, E-mail: aminbadshah@yahoo.com

2016-06-15

This review article presents different fabrication procedures (under the headlines of solvothermal routes, aerosol methods, solution methods and thermolysis), and applications (photocatalytic degradation, ablation of cancer cells, electrode material in lithium ion batteries and in gas sensing, organic solar cells, field emission properties, super capacitor applications, photoelectrochemical performance of QDSCs, photocatalytic reduction of organic pollutants, electrochemical bio sensing, enhanced PEC characteristics of pre-annealed CuS film electrodes) of copper sulfide (Covellite). - Highlights: • This review article presents the synthesis and applications of copper sulfide. • CuS has been used over the years for different applications in nanoscience. • Different syntheticmore » protocols are followed for their preparation which help in the possible modifications in the morphology of CuS.« less

Forms of adsorption and transition states of oxidation of carbon monoxide by molecular oxygen and dissociation of nitrogen monooxide, catalyzed by monovalent copper

NASA Astrophysics Data System (ADS)

Ermakov, A. I.; Mashutin, V. Y.; Vishnjakov, A. V.

With the help of the results of semiempirical (parametric method 3) and ab initio (second-order Møller-Plesset [MP2] unrestricted Hartree-Fock [UHF] 6-31G**, unrestricted density functional theory [UDFT] 6-31G** Becke's three-parameter exchange functional and the gradient-corrected functional of Lee, Yang, and Paar [B3LYP] and UDFT LANL2DZ B3LYP) quantum-chemical calculations has been studied the complexation CO and NO with molecular hydroxide of copper(I). The influence of charge defects has been simulated by the calculations of anionic, neutral, and cationic systems. It is shown that CO and NO are mainly coordinated by nonoxygen atom on an atom of copper(I) hydroxide as one- and two-center forms. These forms are suitable for appearance of prereactionary complexes of catalytic oxidation CO by molecular oxygen and decomposition NO into atoms of nitrogen and oxygen. The corresponding prereactionary complexes for systems with participation of copper(II) hydroxide and copper(III) hydroxide are not revealed. The calculations predict inhibiting impact of copper(II) and copper(III) of the observed reactions. Computed stability of complexes CO and NO with copper(I) hydroxide and activation energy of catalytic conversion of monooxides essentially depend on an excessive charge of the system. Introduction of electron-donating additives into copper(I) hydroxide promotes rise of catalytic activity of copper(I) compound.

The Hydrogenase Activity of the Molybdenum/Copper-containing Carbon Monoxide Dehydrogenase of Oligotropha carboxidovorans*

PubMed Central

Wilcoxen, Jarett; Hille, Russ

2013-01-01

The reaction of the air-tolerant CO dehydrogenase from Oligotropha carboxidovorans with H2 has been examined. Like the Ni-Fe CO dehydrogenase, the enzyme can be reduced by H2 with a limiting rate constant of 5.3 s−1 and a dissociation constant Kd of 525 μm; both kred and kred/Kd, reflecting the breakdown of the Michaelis complex and the reaction of free enzyme with free substrate in the low [S] regime, respectively, are largely pH-independent. During the reaction with H2, a new EPR signal arising from the Mo/Cu-containing active site of the enzyme is observed which is distinct from the signal seen when the enzyme is reduced by CO, with greater g anisotropy and larger hyperfine coupling to the active site 63,65Cu. The signal also exhibits hyperfine coupling to at least two solvent-exchangeable protons of bound substrate that are rapidly exchanged with solvent. Proton coupling is also evident in the EPR signal seen with the dithionite-reduced native enzyme, and this coupling is lost in the presence of bicarbonate. We attribute the coupled protons in the dithionite-reduced enzyme to coordinated water at the copper site in the native enzyme and conclude that bicarbonate is able to displace this water from the copper coordination sphere. On the basis of our results, a mechanism for H2 oxidation is proposed which involves initial binding of H2 to the copper of the binuclear center, displacing the bound water, followed by sequential deprotonation through a copper-hydride intermediate to reduce the binuclear center. PMID:24165123

Copper-Containing Nitrite Reductase Employing Proton-Coupled Spin-Exchanged Electron-Transfer and Multiproton Synchronized Transfer to Reduce Nitrite.

PubMed

Qin, Xin; Deng, Li; Hu, Caihong; Li, Li; Chen, Xiaohua

2017-10-20

The possible catalytic mechanism of the reduction of nitrite by copper-containing nitrite reductases (CuNiRs) is examined by using the M06 function according to two copper models, which include type-one copper (T1Cu) and type-two copper (T2Cu) sites. Examinations confirm that the protonation of two residues, His255 and Asp98, near the T2Cu site, can modulate the redox states of T1Cu and T2Cu, but cannot directly cause electron transfer from T1Cu to T2Cu. The electron hole remains at the T2Cu site when only one residue, His255 or Asp98, is protonated. However, the hole resides at the T1Cu site when both His255 and Asp98 are protonated. Then, the first protonation of nitrite takes place through indirect proton transfer from protonated His255 through the bridging H 2 O and Asp98 with three protons moving together, which cannot cause the cleavage of the HO-NO bond. Subsequently, the substrate is required to obtain another proton from reprotonated His255 through the bridging H 2 O. The reprotonation of nitrite induces the generation of nitric oxide (NO) and H 2 O at the T2Cu site through a special double-proton-coupled spin-exchanged electron-transfer mechanism with indirect proton transfer from His255 to the substrate, a beta-electron of T2Cu I shift to the NO cation, and the remaining alpha-electron changing spin direction at the same time. These results may provide useful information to better understand detailed proton-/electron-transfer reactions for the catalytic processes of CuNiR. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of flower-like micro/nano dual scale structured copper oxide surfaces: Optimization of self-cleaning properties via Taguchi design

NASA Astrophysics Data System (ADS)

Moosavi, Saeideh Sadat; Norouzbeigi, Reza; Velayi, Elmira

2017-11-01

In the present work, copper oxide superhydrophobic surface is fabricated on a copper foil via the chemical bath deposition (CBD) method. The effects of some influential factors such as initial concentrations of Cu (II) ions and the surface energy modifier, solution pH, reaction and modification steps time on the wettability property of copper oxide surface were evaluated using Taguchi L16 experimental design. Results showed that the initial concentration of Cu (II) has the most significant impact on the water contact angle and wettability characteristics. The XRD, SEM, AFM and FTIR analyses were used to characterize the copper oxide surfaces. The Water contact angle (WCA) and contact angle hysteresis (CAH) were also measured. The SEM results indicated the formation of a flower-like micro/nano dual-scale structure of copper oxide on the substrate. This structure composed of numerous nano-petals with a thickness of about 50 nm. As a result, a copper oxide hierarchical surface with WCA of 168.4°± 3.5° and CAH of 2.73° exhibited the best superhydrophobicity under proposed optimum condition. This result has been obtained just by 10 min hydrolysis reaction. Besides, this surface showed a good stability under acidic and saline conditions.

The non-octarepeat copper binding site of the prion protein is a key regulator of prion conversion

NASA Astrophysics Data System (ADS)

Giachin, Gabriele; Mai, Phuong Thao; Tran, Thanh Hoa; Salzano, Giulia; Benetti, Federico; Migliorati, Valentina; Arcovito, Alessandro; Longa, Stefano Della; Mancini, Giordano; D'Angelo, Paola; Legname, Giuseppe

2015-10-01

The conversion of the prion protein (PrPC) into prions plays a key role in transmissible spongiform encephalopathies. Despite the importance for pathogenesis, the mechanism of prion formation has escaped detailed characterization due to the insoluble nature of prions. PrPC interacts with copper through octarepeat and non-octarepeat binding sites. Copper coordination to the non-octarepeat region has garnered interest due to the possibility that this interaction may impact prion conversion. We used X-ray absorption spectroscopy to study copper coordination at pH 5.5 and 7.0 in human PrPC constructs, either wild-type (WT) or carrying pathological mutations. We show that mutations and pH cause modifications of copper coordination in the non-octarepeat region. In the WT at pH 5.5, copper is anchored to His96 and His111, while at pH 7 it is coordinated by His111. Pathological point mutations alter the copper coordination at acidic conditions where the metal is anchored to His111. By using in vitro approaches, cell-based and computational techniques, we propose a model whereby PrPC coordinating copper with one His in the non-octarepeat region converts to prions at acidic condition. Thus, the non-octarepeat region may act as the long-sought-after prion switch, critical for disease onset and propagation.

Layered copper hydroxide n-alkylsulfonate salts: synthesis, characterization, and magnetic behaviors in relation to the basal spacing.

PubMed

Park, Seong-Hun; Lee, Cheol Eui

2005-01-27

A series of hybrid inorganic-organic copper(II) hydroxy n-alkylsulfonate with a triangular lattice, Cu(2)(OH)(3)(C(n)H(2)(n)(+1)SO(3)) (n = 6, 8, 10), are prepared by anion exchange, starting from copper hydroxy nitrate Cu(2)(OH)(3)NO(3). These compounds show a layered structure as determined by X-ray diffraction, with interlayer distances of 14.3-34.8 A in alternation with interdigitated bilayer packing. Magnetic properties have been investigated by means of dc and ac measurements. All the compounds show similar metamagnet behaviors, with a Neel temperature of about 11 K. A subtle difference in the ac magnetic susceptibility among the compounds is understood by the existence of hydrogen bonding between the sulfonate headgroup and the hydroxide anion. A detailed molecular structure of the alkyl chains incorporated to the inorganic copper hydroxide layer is also discussed from the FTIR data.

Chemical constituents of Baeckea frutescens leaves inhibit copper-induced low-density lipoprotein oxidation.

PubMed

Kamiya, Kohei; Satake, Toshiko

2010-04-01

Oxidative modification of LDL plays an important role in the genesis of arteriosclerosis. This study focused on the effects of the leaves of Baeckea frutescens in the prevention of arteriosclerosis. The leaves of B. frutescens have afforded, besides known flavonoid and chromone glycosides, a novel biflavonoid glycoside, characterized as 3-O-alpha-L-rhamnopyranosylmyricetinyl-(I-2'',II-2'')-3-O-alpha-L-rhamnopyranosylmyricetin on the basis of chemical and spectral evidence. This compound exhibited marked inhibition of copper-induced LDL oxidation. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Ultrafast optical modification of exchange interactions in iron oxides

NASA Astrophysics Data System (ADS)

Mikhaylovskiy, R. V.; Hendry, E.; Secchi, A.; Mentink, J. H.; Eckstein, M.; Wu, A.; Pisarev, R. V.; Kruglyak, V. V.; Katsnelson, M. I.; Rasing, Th.; Kimel, A. V.

2015-09-01

Ultrafast non-thermal manipulation of magnetization by light relies on either indirect coupling of the electric field component of the light with spins via spin-orbit interaction or direct coupling between the magnetic field component and spins. Here we propose a scenario for coupling between the electric field of light and spins via optical modification of the exchange interaction, one of the strongest quantum effects with strength of 103 Tesla. We demonstrate that this isotropic opto-magnetic effect, which can be called inverse magneto-refraction, is allowed in a material of any symmetry. Its existence is corroborated by the experimental observation of terahertz emission by spin resonances optically excited in a broad class of iron oxides with a canted spin configuration. From its strength we estimate that a sub-picosecond modification of the exchange interaction by laser pulses with fluence of about 1 mJ cm-2 acts as a pulsed effective magnetic field of 0.01 Tesla.

The exchange interactions and the state of manganese atoms in the solid solutions in Bi{sub 3}NbO{sub 7} of cubic and tetragonal modifications

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Zhuk, N.A.; Korolev, D.A.

2016-01-15

The comparative analysis of magnetic behavior of manganese-containing solid solutions Bi{sub 3}Nb{sub 1−x}Mn{sub x}O{sub 7−δ} (x=0.01−0.10) of cubic and tetragonal modifications was performed. Based on the results of magnetic susceptibility studies paramagnetic manganese atoms in solid solutions of cubic and tetragonal modifications were found to be in the form of Mn(III), Mn(IV) monomers and exchange-coupled dimers of Mn(III)–O–Mn(III), Mn(IV)–O–Mn(IV), Mn(III)–O–Mn(IV). The exchange parameters and the distribution of monomers and dimers in solid solutions as a function of the content of paramagnetic atoms were calculated. - Graphical abstract: Structural transition of cubic to tetragonal Bi{sub 3}NbO{sub 7−δ}.

Global Transcriptional Profiles of the Copper Responses in the Cyanobacterium Synechocystis sp. PCC 6803

PubMed Central

Giner-Lamia, Joaquin; López-Maury, Luis; Florencio, Francisco J.

2014-01-01

Copper is an essential element involved in fundamental processes like respiration and photosynthesis. However, it becomes toxic at high concentration, which has forced organisms to control its cellular concentration. We have recently described a copper resistance system in the cyanobacterium Synechocystis sp. PCC 6803, which is mediated by the two-component system, CopRS, a RND metal transport system, CopBAC and a protein of unknown function, CopM. Here, we report the transcriptional responses to copper additions at non-toxic (0.3 µM) and toxic concentrations (3 µM) in the wild type and in the copper sensitive copR mutant strain. While 0.3 µM copper slightly stimulated metabolism and promoted the exchange between cytochrome c6 and plastocyanin as soluble electron carriers, the addition of 3 µM copper catalyzed the formation of ROS, led to a general stress response and induced expression of Fe-S cluster biogenesis genes. According to this, a double mutant strain copRsufR, which expresses constitutively the sufBCDS operon, tolerated higher copper concentration than the copR mutant strain, suggesting that Fe-S clusters are direct targets of copper toxicity in Synechocystis. In addition we have also demonstrated that InrS, a nickel binding transcriptional repressor that belong to the CsoR family of transcriptional factor, was involved in heavy metal homeostasis, including copper, in Synechocystis. Finally, global gene expression analysis of the copR mutant strain suggested that CopRS only controls the expression of copMRS and copBAC operons in response to copper. PMID:25268225

Iron plaque formation and heavy metal uptake in Spartina alterniflora at different tidal levels and waterlogging conditions.

PubMed

Xu, Yan; Sun, Xiangli; Zhang, Qiqiong; Li, Xiuzhen; Yan, Zhongzheng

2018-05-30

Tidal flat elevation in the estuarine wetland determines the tidal flooding time and flooding frequency, which will inevitably affect the formation of iron plaque and accumulations of heavy metals (HMs) in wetland plants. The present study investigated the formation of iron plaque and HM's (copper, zinc, lead, and chromium) accumulation in S. alterniflora, a typical estuarine wetland species, at different tidal flat elevations (low, middle and high) in filed and at different time (3, 6, 9, 12 h per day) of waterlogging treatment in greenhouse conditions. Results showed that the accumulation of copper, zinc, lead, and chromium in S. alterniflora was proportional to the exchangeable fraction of these metals in the sediments, which generally increased with the increase of waterlogging time, whereas the formations of iron plaque in roots decreased with the increase of waterlogging time. Under field conditions, the uptake of copper and zinc in the different parts of the plants generally increased with the tidal levels despite the decrease in the metals' exchangeable fraction with increasing tidal levels. The formation of iron plaque was found to be highest in the middle tidal positions and significantly lower in low and high tidal positions. Longer waterlogging time increased the metals' accumulation but decreased the formation of iron plaque in S. alterniflora. The binding of metal ions on iron plaque helped impede the uptake and accumulation of copper and chromium in S. alterniflora. Copyright © 2018 Elsevier Inc. All rights reserved.

Current leads cooling for the series-connected hybrid magnets

NASA Astrophysics Data System (ADS)

Bai, Hongyu; Marshall, William S.; Bird, Mark D.; Gavrilin, Andrew V.; Weijers, Hubertus W.

2014-01-01

Two Series-Connected Hybrid (SCH) magnets are being developed at the National High Magnetic Field Laboratory. Both SCH magnets combine a set of resistive Florida-Bitter coils with a superconducting outsert coil constructed of the cable-in-conduit conductor (CICC). The outsert coils of the two magnets employ 20 kA BSCCO HTS current leads for the power supply although they have different designs and cooling methods. The copper heat exchangers of the HTS current leads for the HZB SCH are cooled with forced flow helium at a supply temperature of 44 K, while the copper heat exchangers of HTS current leads for NHMFL SCH are cooled with liquid nitrogen at a temperature of 78 K in a self-demand boil-off mode. This paper presents the two cooling methods and their impacts on cryogenic systems. Their efficiencies and costs are compared and presented.

Analysis of the Importance of Oxides and Clays in Cd, Cr, Cu, Ni, Pb and Zn Adsorption and Retention with Regression Trees

PubMed Central

González-Costa, Juan José; Reigosa, Manuel Joaquín; Matías, José María; Fernández-Covelo, Emma

2017-01-01

This study determines the influence of the different soil components and of the cation-exchange capacity on the adsorption and retention of different heavy metals: cadmium, chromium, copper, nickel, lead and zinc. In order to do so, regression models were created through decision trees and the importance of soil components was assessed. Used variables were: humified organic matter, specific cation-exchange capacity, percentages of sand and silt, proportions of Mn, Fe and Al oxides and hematite, and the proportion of quartz, plagioclase and mica, and the proportions of the different clays: kaolinite, vermiculite, gibbsite and chlorite. The most important components in the obtained models were vermiculite and gibbsite, especially for the adsorption of cadmium and zinc, while clays were less relevant. Oxides are less important than clays, especially for the adsorption of chromium and lead and the retention of chromium, copper and lead. PMID:28072849

Calculation of the exchange coupling constants of copper binuclear systems based on spin-flip constricted variational density functional theory.

PubMed

Zhekova, Hristina R; Seth, Michael; Ziegler, Tom

2011-11-14

We have recently developed a methodology for the calculation of exchange coupling constants J in weakly interacting polynuclear metal clusters. The method is based on unrestricted and restricted second order spin-flip constricted variational density functional theory (SF-CV(2)-DFT) and is here applied to eight binuclear copper systems. Comparison of the SF-CV(2)-DFT results with experiment and with results obtained from other DFT and wave function based methods has been made. Restricted SF-CV(2)-DFT with the BH&HLYP functional yields consistently J values in excellent agreement with experiment. The results acquired from this scheme are comparable in quality to those obtained by accurate multi-reference wave function methodologies such as difference dedicated configuration interaction and the complete active space with second-order perturbation theory. © 2011 American Institute of Physics

78 FR 69470 - Self-Regulatory Organizations; BATS Exchange, Inc.; Notice of Filing and Immediate Effectiveness...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-19

... in BATS Rule 11.13(a)(3)(H). Modifications to Definitions Used for Equities Pricing Tiers The... change to its definitions of ADV and TCV for purposes of BYX tiered pricing.\\13\\ \\12\\ Securities Exchange... strategies at the Exchange's affiliate, BATS Y-Exchange, Inc. (``BYX''); and (2) modify the way that, for...

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1982-01-01

Three chemistry demonstrations are described: (1) modification of copper catalysis demonstration apparatus; (2) experiments in gas-liquid chromatography with simple gas chromatography at room temperature; and (3) equilibria in silver arsenate-arsenic acid and silver phosphate-phosphoric acid systems. Procedures and materials needed are provided.…

Data Analysis for Ocean Thermal Energy Conversion (otec)

DTIC Science & Technology

1979-11-01

the OTEC system consisted of copper heater cylinders which were press fitted to the outside of the heat exchanger tubes. Voltage to the heaters was...INFORMATION The Heat Exchanger Heating task was sponsored by the Department of Energy under Interagency Agreement ET-78-I-O1-3218, Task Number 13218, Work...Panama City, Florida. Test site characterization, cleaning systems, and the physical structure of the OTEC system are discussed briefly. Data sampling

Copper Alloy For High-Temperature Uses

NASA Technical Reports Server (NTRS)

Dreshfield, Robert L.; Ellis, David L.; Michal, Gary

1994-01-01

Alloy of Cu/8Cr/4Nb (numbers indicate parts by atom percent) improved over older high-temperature copper-based alloys in that it offers enhanced high temperature strength, resistance to creep, and ductility while retaining most of thermal conductivity of pure copper; in addition, alloy does not become embrittled upon exposure to hydrogen at temperatures as high as 705 degrees C. Designed for use in presence of high heat fluxes and active cooling; for example, in heat exchangers in advanced aircraft and spacecraft engines, and other high-temperature applications in which there is need for such material. High conductivity and hardness of alloy exploited in welding electrodes and in high-voltage and high-current switches and other applications in which wear poses design problem.

Production of sodium-22 from proton irradiated aluminum

DOEpatents

Taylor, Wayne A.; Heaton, Richard C.; Jamriska, David J.

1996-01-01

A process for selective separation of sodium-22 from a proton irradiated minum target including dissolving a proton irradiated aluminum target in hydrochloric acid to form a first solution including aluminum ions and sodium ions, separating a portion of the aluminum ions from the first solution by crystallization of an aluminum salt, contacting the remaining first solution with an anion exchange resin whereby ions selected from the group consisting of iron and copper are selectively absorbed by the anion exchange resin while aluminum ions and sodium ions remain in solution, contacting the solution with an cation exchange resin whereby aluminum ions and sodium ions are adsorbed by the cation exchange resin, and, contacting the cation exchange resin with an acid solution capable of selectively separating the adsorbed sodium ions from the cation exchange resin while aluminum ions remain adsorbed on the cation exchange resin is disclosed.

Terrestrial Eco-Toxicological Tests as Screening Tool to Assess Soil Contamination in Krompachy Area

NASA Astrophysics Data System (ADS)

Ol'ga, Šestinová; Findoráková, Lenka; Hančuľák, Jozef; Fedorová, Erika; Tomislav, Špaldon

2016-10-01

In this study, we present screening tool of heavy metal inputs to agricultural and permanent grass vegetation of the soils in Krompachy. This study is devoted to Ecotoxicity tests, Terrestrial Plant Test (modification of OECD 208, Phytotoxkit microbiotest on Sinapis Alba) and chronic tests of Earthworm (Dendrobaena veneta, modification of OECD Guidelines for the testing of chemicals 317, Bioaccumulation in Terrestrial Oligochaetes) as practical and sensitive screening method for assessing the effects of heavy metals in Krompachy soils. The total Cu, Zn, As, Pb and Hg concentrations and eco-toxicological tests of soils from the Krompachy area were determined of 4 sampling sites in 2015. An influence of the sampling sites distance from the copper smeltery on the absolutely concentrations of metals were recorded for copper, lead, zinc, arsenic and mercury. The highest concentrations of these metals were detected on the sampling sites up to 3 km from the copper smeltery. The samples of soil were used to assess of phytotoxic effect. Total mortality was established at earthworms using chronic toxicity test after 7 exposure days. The results of our study confirmed that no mortality was observed in any of the study soils. Based on the phytotoxicity testing, phytotoxic effects of the metals contaminated soils from the samples 3KR (7-9) S.alba seeds was observed.

Copper circuit patterning on polymer using selective surface modification and electroless plating

NASA Astrophysics Data System (ADS)

Park, Sang Jin; Ko, Tae-Jun; Yoon, Juil; Moon, Myoung-Woon; Oh, Kyu Hwan; Han, Jun Hyun

2017-02-01

We have examined a potential new and simple method for patterning a copper circuit on PET substrate by copper electroless plating, without the pretreatment steps (i.e., sensitization and activation) for electroless plating as well as the etching processes of conventional circuit patterning. A patterned mask coated with a catalyst material, Ag, for the reduction of Cu ions, is placed on a PET substrate. Subsequent oxygen plasma treatment of the PET substrate covered with the mask promotes the selective generation of anisotropic pillar- or hair-like nanostructures coated with co-deposited nanoparticles of the catalyst material on PET. After oxygen plasma treatment, a Cu circuit is well formed just by dipping the plasma-treated PET into a Cu electroless plating solution. By increasing the oxygen gas pressure in the chamber, the height of the nanostructures increases and the Ag catalyst particles are coated on not only the top but also the side surfaces of the nanostructures. Strong mechanical interlocking between the Cu circuit and PET substrate is produced by the large surface area of the nanostructures, and enhances peel strength. Results indicate this new simple two step (plasma surface modification and pretreatment-free electroless plating) method can be used to produce a flexible Cu circuit with good adhesion.

Biosorption of copper and lead ions by waste beer yeast.

PubMed

Han, Runping; Li, Hongkui; Li, Yanhu; Zhang, Jinghua; Xiao, Huijun; Shi, Jie

2006-10-11

Locally available waste beer yeast, a byproduct of brewing industry, was found to be a low cost and promising adsorbent for adsorbing copper and lead ions from wastewater. In this work, biosorption of copper and lead ions on waste beer yeast was investigated in batch mode. The equilibrium adsorptive quantity was determined to be a function of the solution pH, contact time, beer yeast concentration, salt concentration and initial concentration of copper and lead ions. The experimental results were fitted well to the Langmuir and Freundlich model isotherms. According to the parameters of Langmuir isotherm, the maximum biosorption capacities of copper and lead ions onto beer yeast were 0.0228 and 0.0277 mmol g(-1) at 293 K, respectively. The negative values of the standard free energy change (DeltaG degrees ) indicate spontaneous nature of the process. Competitive biosorption of two metal ions was investigated in terms of sorption quantity. The amount of one metal ion adsorbed onto unit weight of biosorbent (q(e)) decreased with increasing the competing metal ion concentration. The binding capacity for lead is more than for copper. Ion exchange is probably one of the main mechanism during adsorptive process.

Fabrication of a wettability-gradient surface on copper by screen-printing techniques

NASA Astrophysics Data System (ADS)

Huang, Ding-Jun; Leu, Tzong-Shyng

2015-08-01

In this study, a screen-printing technique is utilized to fabricate a wettability-gradient surface on a copper substrate. The pattern definitions on the copper surface were freely fabricated to define the regions with different wettabilities, for which the printing definition technique was developed as an alternative to the existing costly photolithography techniques. This fabrication process using screen printing in tandem with chemical modification methods can easily realize an excellent wettability-gradient surface with superhydrophobicity and superhydrophilicity. Surface analyses were performed to characterize conditions in some fabrication steps. A water droplet movement sequence is provided to clearly demonstrate the droplet-driving effectiveness of the fabricated gradient surface. The droplet-driving efficiency offers a promising solution for condensation heat transfer applications in the foreseeable future.

Therapeutic potential of copper chelation with triethylenetetramine in managing diabetes mellitus and Alzheimer's disease.

PubMed

Cooper, Garth J S

2011-07-09

This article reviews recent evidence, much of which has been generated by my group's research programme, which has identified for the first time a previously unknown copper-overload state that is central to the pathogenesis of diabetic organ damage. This state causes tissue damage in the blood vessels, heart, kidneys, retina and nerves through copper-mediated oxidative stress. This author now considers this copper-overload state to provide an important new target for therapeutic intervention, the objective of which is to prevent or reverse the diabetic complications. Triethylenetetramine (TETA) has recently been identified as the first in a new class of anti-diabetic molecules through the original work reviewed here, thus providing a new use for this molecule, which was previously approved by the US FDA in 1985 as a second-line treatment for Wilson's disease. TETA acts as a highly selective divalent copper (Cu(II)) chelator that prevents or reverses diabetic copper overload, thereby suppressing oxidative stress. TETA treatment of diabetic animals and patients has identified and quantified the interlinked defects in copper metabolism that characterize this systemic copper overload state. Copper overload in diabetes mellitus differs from that in Wilson's disease through differences in their respective causative molecular mechanisms, and resulting differences in tissue localization and behaviour of the excess copper. Elevated pathogenetic tissue binding of copper occurs in diabetes. It may well be mediated by advanced-glycation endproduct (AGE) modification of susceptible amino-acid residues in long-lived fibrous proteins, for example, connective tissue collagens in locations such as blood vessel walls. These AGE modifications can act as localized, fixed endogenous chelators that increase the chelatable-copper content of organs such as the heart and kidneys by binding excessive amounts of catalytically active Cu(II) in specific vascular beds, thereby focusing the related copper-mediated oxidative stress in susceptible tissues. In this review, summarized evidence from our clinical studies in healthy volunteers and diabetic patients with left-ventricular hypertrophy, and from nonclinical models of diabetic cardiac, arterial, renal and neural disease is used to construct descriptions of the mechanisms by which TETA treatment prevents injury and regenerates damaged organs. Our recent phase II proof-of-principle studies in patients with type 2 diabetes and in nonclinical models of diabetes have helped to define the pathogenetic defects in copper regulation, and have shown that they are reversible by TETA. The drug tightly binds and extracts excess systemic Cu(II) into the urine whilst neutralizing its catalytic activity, but does not cause systemic copper deficiency, even after prolonged use. Its physicochemical properties, which are pivotal for its safety and efficacy, clearly differentiate it from all other clinically available transition metal chelators, including D-penicillamine, ammonium tetrathiomolybdate and clioquinol. The studies reviewed here show that TETA treatment is generally effective in preventing or reversing diabetic organ damage, and support its ongoing development as a new medicine for diabetes. Trientine (TETA dihydrochloride) has been used since the mid-1980s as a second-line treatment for Wilson's disease, and our recent clinical studies have reinforced the impression that it is likely to be safe for long-term use in patients with diabetes and related metabolic disorders. There is substantive evidence to support the view that diabetes shares many pathogenetic mechanisms with Alzheimer's disease and vascular dementia. Indeed, the close epidemiological and molecular linkages between them point to Alzheimer's disease/vascular dementia as a further therapeutic target where experimental pharmacotherapy with TETA could well find further clinical application.

An investigation of roof runoff during rain events at the Royal Military College of Canada and potential discharge to Lake Ontario.

PubMed

Kelly, David G; Weir, Ron D; White, Steven D

2011-01-01

The Royal Military College of Canada, located on the north eastern shore of Lake Ontario, possesses an abundance of copper roofs and lacks surface water treatment prior to discharge into Lake Ontario. Rainwater, roof runoff and soil samples were collected and analyzed for copper and other parameters. Copper was consistently detected in runoff samples with average concentrations of 3200 +/- 2100 microg/L. Multivariable linear regression analysis for a dependant copper runoff concentration yielded an adjusted R2 value of 0.611, based on an independent variable model using minimum temperature, maximum temperature, total precipitation, and wind speed. Lake water samples taken in the vicinity of storm water outfalls draining areas with copper roofs ranged from 2.0 to 40 microg/L copper. Such data exceed the 2.0 microg/L Canadian Water Quality Guidelines for the Protection of Aquatic Life as outlined by the Canadian Council of Ministers of the Environment (CCME). Analysis of raw, filtered and digested forms suggested that the majority of copper present in runoff and lake water samples was in a dissolved form. The majority of soils taken in this study displayed copper concentrations below the 63 microg/g CCME residential/parkland land use limits. These findings suggested that ion exchange processes between runoff water and soil do not occur to a sufficient extent to elevate copper levels in soil. It may therefore be concluded that the eventual fate of copper, which is not discharged via storm water outfalls, is lost to the water table and Lake Ontario through the sub-soil.

75 FR 34192 - Self-Regulatory Organizations; NYSE Arca, Inc.; Notice of Filing and Immediate Effectiveness of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-16

... erroneous trades occurring from disruptions and/or malfunctions of Exchange systems. The changes described... disruptions and malfunctions. Specifically, the Exchange proposes to include ``verifiable systems disruptions... modification of transactions that resulted from verifiable disruptions and/or malfunctions of Exchanges systems...

THE EFFECT OF SALINITY ON RATES OF ELEMENTAL MERCURY AIR/WATER EXCHANGE

EPA Science Inventory

The U.S. EPA laboratory in Athens, Georgia i spursuing the goal of developing a model for describing toxicant vapor phase air/water exchange under all relevant environmental conditions. To date, the two-layer exchange model (suitable for low wind speed conditions) has been modif...

Copper-resistant bacteria reduces oxidative stress and uptake of copper in lentil plants: potential for bacterial bioremediation.

PubMed

Islam, Faisal; Yasmeen, Tahira; Ali, Qasim; Mubin, Muhammad; Ali, Shafaqat; Arif, Muhammad Saleem; Hussain, Sabir; Riaz, Muhammad; Abbas, Farhat

2016-01-01

For effective microbe-assisted bioremediation, metal-resistant plant growth-promoting bacteria (PGPB) must facilitate plant growth by restricting excess metal uptake in plants, leading to prevent its bio-amplification in the ecosystem. The aims of our study were to isolate and characterize copper (Cu)-resistant PGPB from waste water receiving contaminated soil. In addition, we investigated the phytotoxic effect of copper on the lentil plants inoculated with copper-resistant bacteria Providencia vermicola, grown in copper-contaminated soil. Copper-resistant P. vermicola showed multiple plant growth promoting characteristics, when used as a seed inoculant. It protected the lentil plants from copper toxicity with a considerable increase in root and shoot length, plant dry weight and leaf area. A notable increase in different gas exchange characteristics such as A, E, C i , g s , and A/E, as well as increase in N and P accumulation were also recorded in inoculated plants as compared to un-inoculated copper stressed plants. In addition, leaf chlorophyll content, root nodulation, number of pods, 1,000 seed weight were also higher in inoculated plants as compared with non-inoculated ones. Anti-oxidative defense mechanism improved significantly via elevated expression of reactive oxygen species -scavenging enzymes including ascorbate peroxidase, superoxide dismutase, catalase, and guaiacol peroxidase with alternate decrease in malondialdehyde and H2O2 contents, reduced electrolyte leakage, proline, and total phenolic contents suggesting that inoculation of P. vermicola triggered heavy metals stress-related defense pathways under copper stress. Overall, the results demonstrated that the P. vermicola seed inoculation confer heavy metal stress tolerance in lentil plant which can be used as a potent biotechnological tool to cope with the problems of copper pollution in crop plants for better yield.

Methanobactin and the Link between Copper and Bacterial Methane Oxidation

PubMed Central

Semrau, Jeremy D.; Murrell, J. Colin; Gallagher, Warren H.; Dennison, Christopher; Vuilleumier, Stéphane

2016-01-01

SUMMARY Methanobactins (mbs) are low-molecular-mass (<1,200 Da) copper-binding peptides, or chalkophores, produced by many methane-oxidizing bacteria (methanotrophs). These molecules exhibit similarities to certain iron-binding siderophores but are expressed and secreted in response to copper limitation. Structurally, mbs are characterized by a pair of heterocyclic rings with associated thioamide groups that form the copper coordination site. One of the rings is always an oxazolone and the second ring an oxazolone, an imidazolone, or a pyrazinedione moiety. The mb molecule originates from a peptide precursor that undergoes a series of posttranslational modifications, including (i) ring formation, (ii) cleavage of a leader peptide sequence, and (iii) in some cases, addition of a sulfate group. Functionally, mbs represent the extracellular component of a copper acquisition system. Consistent with this role in copper acquisition, mbs have a high affinity for copper ions. Following binding, mbs rapidly reduce Cu2+ to Cu1+. In addition to binding copper, mbs will bind most transition metals and near-transition metals and protect the host methanotroph as well as other bacteria from toxic metals. Several other physiological functions have been assigned to mbs, based primarily on their redox and metal-binding properties. In this review, we examine the current state of knowledge of this novel type of metal-binding peptide. We also explore its potential applications, how mbs may alter the bioavailability of multiple metals, and the many roles mbs may play in the physiology of methanotrophs. PMID:26984926

Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations.

PubMed

Liu, Qian; Wu, Kangkang; Tang, Fei; Yao, Lihua; Yang, Fei; Nie, Zhou; Yao, Shouzhuo

2009-09-28

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

The influence of EI-21 redox ion-exchange resins on the secondary-coolant circuit water chemistry of vehicular nuclear power installations

NASA Astrophysics Data System (ADS)

Moskvin, L. N.; Rakov, V. T.

2015-06-01

The results obtained from testing the secondary-coolant circuit water chemistry of full-scale land-based prototype bench models of vehicular nuclear power installations equipped with water-cooled water-moderated and liquid-metal reactor plants are presented. The influence of copper-containing redox ionexchange resins intended for chemically deoxygenating steam condensate on the working fluid circulation loop's water chemistry is determined. The influence of redox ion-exchange resins on the water chemistry is evaluated by generalizing an array of data obtained in the course of extended monitoring using the methods relating to physicochemical analysis of the quality of condensate-feedwater path media and the methods relating to metallographic analysis of the state of a faulty steam generator's tube system surfaces. The deoxygenating effectiveness of the normal state turbine condensate vacuum deaeration system is experimentally determined. The refusal from applying redox ion-exchange resins in the condensate polishing ion-exchange filters is formulated based on the obtained data on the adverse effect of copper-containing redox ionexchange resins on the condensate-feedwater path water chemistry and based on the data testifying a sufficient effect from using the normal state turbine condensate vacuum deaeration system. Data on long-term operation of the prototype bench model of a vehicular nuclear power installation without subjecting the turbine condensate to chemical deoxygenation are presented.

Strong Cation Exchange Chromatography in Analysis of Posttranslational Modifications: Innovations and Perspectives

PubMed Central

Edelmann, Mariola J.

2011-01-01

Strong cation exchange (SCX) chromatography has been utilized as an excellent separation technique that can be combined with reversed-phase (RP) chromatography, which is frequently used in peptide mass spectrometry. Although SCX is valuable as the second component of such two-dimensional separation methods, its application goes far beyond efficient fractionation of complex peptide mixtures. Here I describe how SCX facilitates mapping of the protein posttranslational modifications (PTMs), specifically phosphorylation and N-terminal acetylation. The SCX chromatography has been mainly used for enrichment of these two PTMs, but it might also be beneficial for high-throughput analysis of other modifications that alter the net charge of a peptide. PMID:22174558

Dynamics of the sorption of copper(II) and silver(I) by materials based on sulfoethylchitosan with various degrees of crosslinking

NASA Astrophysics Data System (ADS)

Petrova, Yu. S.; Pestov, A. V.; Alifkhanova, L. M. k.; Neudachina, L. K.

2017-04-01

Optimum conditions of the dynamic concentration of copper(II) and silver(I) ions simultaneously present in a solution with N-(2-sulfoethyl)chitosan with a degree of modification equal to 0.5 and different degrees of crosslinking by glutaraldehyde are determined. The values of coefficients of selectivity K Ag/Cu are determined under dynamic conditions. It is shown that the selectivity of the sorption of silver(I) increases (compared to copper(II)) as the degree of crosslinking of sorbents based on N-(2-sulfoethyl)chitosan is raised. Mathematical treatment of the obtained dynamic curves is performed according to the Thomas, Adams-Bohart, and Yoon and Nelson models. As a result, the values of dynamic capacity of sorbents, the rate constant of the reaction, and the release time of 50% of the sorbate are determined. The quantitative desorption of copper and silver from the surface of sorbents is achieved by using 1 mol/dm3 solution of nitric acid.

Spectroscopic investigation of different concentrations of the vapour deposited copper phthalocyanine as a "guest" in polyimide matrix.

PubMed

Georgiev, Anton; Yordanov, Dancho; Dimov, Dean; Assa, Jacob; Spassova, Erinche; Danev, Gencho

2015-04-05

Nanocomposite layers 250 nm copper phthalocyanine/polyimide prepared by simultaneous vapour deposition of three different sources were studied. Different concentrations of copper phthalocyanine as a "guest" in polyimide matrix as a function of conditions of the preparation have been determined by FTIR (Fourier Transform Infrared) and UV-VIS (Ultraviolet-Visible) spectroscopies. The aim was to estimate the possibility of the spectroscopic methods for quantitative determination of the "guest" and compare with the quality of the polyimide thin films in relation to the "guest" concentration. The band at 1334 cm(-1) has been used for quantitative estimation of "guest" in polyimide matrix. The concentrations of the copper phthalocyanine less than 20% require curve fitting techniques with Fourier self deconvolution. The relationship between "guest" concentrations and degree of imidization, as well as the electronic UV-VIS spectra are discussed in relation to the composition, imidization degree and the two crystallographic modification of the embedded chromophore. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of long term organic amendments and vegetation of vineyard soils on the microscale distribution and biogeochemistry of copper.

PubMed

Navel, Aline; Martins, Jean M F

2014-01-01

In this study we evaluated the effect of the long term organic management of a vineyard-soil on the biogeochemistry of copper at the micro-aggregate scale. The model vineyard-soil (Mâcon-France) experienced a long-term field-experiment that consisted in amendments and vegetations with various materials and plants. We studied specifically the effect of Straw (S) and Conifer Compost (CC) organic amendments and Clover (Cl) and Fescue (F) vegetation on the fate of copper (fungicide) in the surface layer of this loamy soil, through a comparison with the Non Amended soil (NA). After collection the five soils were immediately physically fractionated in order to obtain 5 granulometric size-fractions. All soils and size-fractions were quantitatively characterized in terms of granulometry, chemical content and copper distribution, speciation and bioavailability to bacteria and plants. The results showed strong increases of soil-constituents aggregation for all treatments (Cl>CC>S>F>NA), in relation with the increased cementation of soil-constituents by organic matter (OM). The distribution patterns of all major elements and organic carbon were found highly variable within the soil sub-fractions and also between the 5 treatments. Due to their specific inorganic and organic composition, soil sub-fractions can thus be considered as a specific microbial habitat. Added OM accumulated preferentially in the 20-2 μm and in the >250 μm of the 5 soils. The distribution patterns of copper as well as its speciation and bioavailability to bacteria in the soil sub-fractions were shown to be strongly different among the five soils, in relation with OM distribution. Our results also suggest that Cu-bioavailability to plants is controlled by soil-rhizosphere structure. Altogether our results permitted to show that long-term organic management of a vineyard soil induced stable modifications of soil physical and chemical properties at both macro and micro-scales. These modifications affected in turn the micro-scale biogeochemistry of copper, and especially its bioavailability to bacteria and plants. © 2013.

Superhydrophobic Copper Surfaces with Anticorrosion Properties Fabricated by Solventless CVD Methods.

PubMed

Vilaró, Ignasi; Yagüe, Jose L; Borrós, Salvador

2017-01-11

Due to continuous miniaturization and increasing number of electrical components in electronics, copper interconnections have become critical for the design of 3D integrated circuits. However, corrosion attack on the copper metal can affect the electronic performance of the material. Superhydrophobic coatings are a commonly used strategy to prevent this undesired effect. In this work, a solventless two-steps process was developed to fabricate superhydrophobic copper surfaces using chemical vapor deposition (CVD) methods. The superhydrophobic state was achieved through the design of a hierarchical structure, combining micro-/nanoscale domains. In the first step, O 2 - and Ar-plasma etchings were performed on the copper substrate to generate microroughness. Afterward, a conformal copolymer, 1H,1H,2H,2H-perfluorodecyl acrylate-ethylene glycol diacrylate [p(PFDA-co-EGDA)], was deposited on top of the metal via initiated CVD (iCVD) to lower the surface energy of the surface. The copolymer topography exhibited a very characteristic and unique nanoworm-like structure. The combination of the nanofeatures of the polymer with the microroughness of the copper led to achievement of the superhydrophobic state. AFM, SEM, and XPS were used to characterize the evolution in topography and chemical composition during the CVD processes. The modified copper showed water contact angles as high as 163° and hysteresis as low as 1°. The coating withstood exposure to aggressive media for extended periods of time. Tafel analysis was used to compare the corrosion rates between bare and modified copper. Results indicated that iCVD-coated copper corrodes 3 orders of magnitude slower than untreated copper. The surface modification process yielded repeatable and robust superhydrophobic coatings with remarkable anticorrosion properties.

Erosion and Modifications of Tungsten-Coated Carbon and Copper Under High Heat Flux

NASA Astrophysics Data System (ADS)

Liu, Xiang; S, Tamura; K, Tokunaga; N, Yoshida; Zhang, Fu; Xu, Zeng-yu; Ge, Chang-chun; N, Noda

2003-08-01

Tungsten-coated carbon and copper was prepared by vacuum plasma spraying (VPS) and inert gas plasma spraying (IPS), respectively. W/CFC (Tungsten/Carbon Fiber-Enhanced material) coating has a diffusion barrier that consists of W and Re multi-layers pre-deposited by physical vapor deposition on carbon fiber-enhanced materials, while W/Cu coating has a graded transition interface. Different grain growth processes of tungsten coatings under stable and transient heat loads were observed, their experimental results indicated that the recrystallizing temperature of VPS-W coating was about 1400 °C and a recrystallized columnar layer of about 30 μm thickness was formed by cyclic heat loads of 4 ms pulse duration. Erosion and modifications of W/CFC and W/Cu coatings under high heat load, such as microstructure changes of interface, surface plastic deformations and cracks, were investigated, and the erosion mechanism (erosion products) of these two kinds of tungsten coatings under high heat flux was also studied.

Immobilized copper(II) macrocyclic complex on MWCNTs with antibacterial activity

NASA Astrophysics Data System (ADS)

Tarlani, Aliakbar; Narimani, Khashayar; Mohammadipanah, Fatemeh; Hamedi, Javad; Tahermansouri, Hasan; Amini, Mostafa M.

2015-06-01

In a new approach, a copper(II) tetraaza macrocyclic complex (CuTAM) was covalently bonded on modified multi-walled carbon nanotubes (MWCNTs). To achieve this purpose, MWCNTs were converted to MWCNT-COCl and then reacted to NH groups of TAM ligand. The prepared material was characterized by Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and FESEM (field emission scanning electron microscopy). FT-IR and TGA demonstrated the presence of the organic moieties, and XRD proved that the structure of MWCNTs remained intact during the three modification steps. An increase in the ID/IG ratio in Raman spectra confirmed the surface modifications. Finally, the samples were subjected to an antibacterial assessment to compare their biological activity. The antibacterial test showed that the grafted complex on the surface of the nanotube (MWCNT-CO-CuTAM) has higher antibacterial activity against Bacillus subtilis ATCC 6633 than the MWCNT-COOH and CuTAM with 1000 and 2000 μg/mL.

Description and performance of a novel aqueous all-copper redox flow battery

NASA Astrophysics Data System (ADS)

Sanz, Laura; Lloyd, David; Magdalena, Eva; Palma, Jesús; Kontturi, Kyösti

2014-12-01

In this paper we present a novel aqueous redox flow battery chemistry based on copper chloro complexes. The energy density (20 Wh L-1) achieved is comparable to traditional vanadium redox flow batteries. This is due to the high solubility of copper (3 M), which offsets the relatively low cell potential (0.6 V). The electrolyte is cheap, simple to prepare and easy to recycle since no additives or catalysts are used. The stack used is based on plain graphite electrode materials and a low-cost microporous separator. The system can be operated at 60 °C eliminating the need for a heat exchanger and delivers an energy efficiency of 93, 86 and 74% at 5, 10 and 20 mA cm-2 respectively.

Ultrafast optical modification of exchange interactions in iron oxides

PubMed Central

Mikhaylovskiy, R.V.; Hendry, E.; Secchi, A.; Mentink, J.H.; Eckstein, M.; Wu, A.; Pisarev, R.V.; Kruglyak, V.V.; Katsnelson, M.I.; Rasing, Th.; Kimel, A.V.

2015-01-01

Ultrafast non-thermal manipulation of magnetization by light relies on either indirect coupling of the electric field component of the light with spins via spin-orbit interaction or direct coupling between the magnetic field component and spins. Here we propose a scenario for coupling between the electric field of light and spins via optical modification of the exchange interaction, one of the strongest quantum effects with strength of 103 Tesla. We demonstrate that this isotropic opto-magnetic effect, which can be called inverse magneto-refraction, is allowed in a material of any symmetry. Its existence is corroborated by the experimental observation of terahertz emission by spin resonances optically excited in a broad class of iron oxides with a canted spin configuration. From its strength we estimate that a sub-picosecond modification of the exchange interaction by laser pulses with fluence of about 1 mJ cm−2 acts as a pulsed effective magnetic field of 0.01 Tesla. PMID:26373688

Ultrafast optical modification of exchange interactions in iron oxides.

PubMed

Mikhaylovskiy, R V; Hendry, E; Secchi, A; Mentink, J H; Eckstein, M; Wu, A; Pisarev, R V; Kruglyak, V V; Katsnelson, M I; Rasing, Th; Kimel, A V

2015-09-16

Ultrafast non-thermal manipulation of magnetization by light relies on either indirect coupling of the electric field component of the light with spins via spin-orbit interaction or direct coupling between the magnetic field component and spins. Here we propose a scenario for coupling between the electric field of light and spins via optical modification of the exchange interaction, one of the strongest quantum effects with strength of 10(3) Tesla. We demonstrate that this isotropic opto-magnetic effect, which can be called inverse magneto-refraction, is allowed in a material of any symmetry. Its existence is corroborated by the experimental observation of terahertz emission by spin resonances optically excited in a broad class of iron oxides with a canted spin configuration. From its strength we estimate that a sub-picosecond modification of the exchange interaction by laser pulses with fluence of about 1 mJ cm(-2) acts as a pulsed effective magnetic field of 0.01 Tesla.

Effects of Copper Addition on Copper Resistance, Antibiotic Resistance Genes, and intl1 during Swine Manure Composting

PubMed Central

Yin, Yanan; Gu, Jie; Wang, Xiaojuan; Song, Wen; Zhang, Kaiyu; Sun, Wei; Zhang, Xin; Zhang, Yajun; Li, Haichao

2017-01-01

Copper is one of the most abundant heavy metals present in swine manure. In this study, a laboratory-scale aerobic composting system was amended with Cu at three levels (0, 200, and 2000 mg kg-1, i.e., control, Cu200, and Cu2000 treatments, respectively) to determine its effect on the fate of copper resistance genes [copper resistance genes (CRGs): pcoA, cusA, copA, and tcrB], antibiotic resistance genes [antibiotic resistance genes (ARGs): erm(A) and erm(B)], and intl1. The results showed that the absolute abundances of pcoA, tcrB, erm(A), erm(B), and intl1 were reduced, whereas those of copA and cusA increased after swine manure composting. Redundancy analysis showed that temperature significantly affected the variations in CRGs, ARGs, and intl1. The decreases in CRGs, ARGs, and intI1 were positively correlated with the exchangeable Cu levels. The bacterial community could be grouped according to the composting time under different treatments, where the high concentration of copper had a more persistent effect on the bacterial community. Network analysis determined that the co-occurrence of CRGs, ARGs, and intI1, and the bacterial community were the main contributors to the changes in CRGs, ARG, and intl1. Thus, temperature, copper, and changes in the bacterial community composition had important effects on the variations in CRGs, ARGs, and intl1 during manure composting in the presence of added copper. PMID:28316595

Phosphorylation of amyloid precursor protein at threonine 668 is essential for its copper-responsive trafficking in SH-SY5Y neuroblastoma cells.

PubMed

Acevedo, Karla M; Opazo, Carlos M; Norrish, David; Challis, Leesa M; Li, Qiao-Xin; White, Anthony R; Bush, Ashley I; Camakaris, James

2014-04-18

Amyloid precursor protein (APP) undergoes post-translational modification, including O- and N-glycosylation, ubiquitination, and phosphorylation as it traffics through the secretory pathway. We have previously reported that copper promotes a change in the cellular localization of APP. We now report that copper increases the phosphorylation of endogenous APP at threonine 668 (Thr-668) in SH-SY5Y neuronal cells. The level of APPT668-p (detected using a phospho-site-specific antibody) exhibited a copper-dependent increase. Using confocal microscopy imaging we demonstrate that the phospho-deficient mutant, Thr-668 to alanine (T668A), does not exhibit detectable copper-responsive APP trafficking. In contrast, mutating a serine to an alanine at residue 655 does not affect copper-responsive trafficking. We further investigated the importance of the Thr-668 residue in copper-responsive trafficking by treating SH-SY5Y cells with inhibitors for glycogen synthase kinase 3-β (GSK3β) and cyclin-dependent kinases (Cdk), the main kinases that phosphorylate APP at Thr-668 in neurons. Our results show that the GSK3β kinase inhibitors LiCl, SB 216763, and SB 415286 prevent copper-responsive APP trafficking. In contrast, the Cdk inhibitors Purvalanol A and B had no significant effect on copper-responsive trafficking in SH-SY5Y cells. In cultured primary hippocampal neurons, copper promoted APP re-localization to the axon, and this effect was inhibited by the addition of LiCl, indicating that a lithium-sensitive kinase(s) is involved in copper-responsive trafficking in hippocampal neurons. This is consistent with APP axonal transport to the synapse, where APP is involved in a number of functions. We conclude that copper promotes APP trafficking by promoting a GSK3β-dependent phosphorylation in SH-SY5Y cells.

Phosphorylation of Amyloid Precursor Protein at Threonine 668 Is Essential for Its Copper-responsive Trafficking in SH-SY5Y Neuroblastoma Cells*

PubMed Central

Acevedo, Karla M.; Opazo, Carlos M.; Norrish, David; Challis, Leesa M.; Li, Qiao-Xin; White, Anthony R.; Bush, Ashley I.; Camakaris, James

2014-01-01

Amyloid precursor protein (APP) undergoes post-translational modification, including O- and N-glycosylation, ubiquitination, and phosphorylation as it traffics through the secretory pathway. We have previously reported that copper promotes a change in the cellular localization of APP. We now report that copper increases the phosphorylation of endogenous APP at threonine 668 (Thr-668) in SH-SY5Y neuronal cells. The level of APPT668-p (detected using a phospho-site-specific antibody) exhibited a copper-dependent increase. Using confocal microscopy imaging we demonstrate that the phospho-deficient mutant, Thr-668 to alanine (T668A), does not exhibit detectable copper-responsive APP trafficking. In contrast, mutating a serine to an alanine at residue 655 does not affect copper-responsive trafficking. We further investigated the importance of the Thr-668 residue in copper-responsive trafficking by treating SH-SY5Y cells with inhibitors for glycogen synthase kinase 3-β (GSK3β) and cyclin-dependent kinases (Cdk), the main kinases that phosphorylate APP at Thr-668 in neurons. Our results show that the GSK3β kinase inhibitors LiCl, SB 216763, and SB 415286 prevent copper-responsive APP trafficking. In contrast, the Cdk inhibitors Purvalanol A and B had no significant effect on copper-responsive trafficking in SH-SY5Y cells. In cultured primary hippocampal neurons, copper promoted APP re-localization to the axon, and this effect was inhibited by the addition of LiCl, indicating that a lithium-sensitive kinase(s) is involved in copper-responsive trafficking in hippocampal neurons. This is consistent with APP axonal transport to the synapse, where APP is involved in a number of functions. We conclude that copper promotes APP trafficking by promoting a GSK3β-dependent phosphorylation in SH-SY5Y cells. PMID:24610780

Impact of Arsenic Treatment Techniques on Distribution Water Quality

EPA Science Inventory

This presentation will summarize the results of the distribution water quality studies (arsenic, lead, and copper) of the demonstration program. The impact of the treatment systems by type of system (adsorptive media, coagulation/filtration, ion exchange, etc) will be shown by co...

Surface modification of calcium-copper hydroxyapatites using polyaspartic acid

NASA Astrophysics Data System (ADS)

Othmani, Masseoud; Aissa, Abdallah; Bachoua, Hassen; Debbabi, Mongi

2013-01-01

Mixed calcium-copper hydroxyapatite (Ca-CuHAp), with general formula Ca(10-x)Cux(PO4)6(OH)2, where 0 ≤ x ≤ 0.75 was prepared in aqueous medium in the presence of different concentrations of poly-L-aspartic acid (PASP). XRD, IR, TG-DTA, TEM-EDX, AFM and chemical analyses were used to characterize the structure, morphology and composition of the products. All techniques show the formation of new hybrid compounds Ca-CuHAp-PASP. The presence of the grafting moiety on the apatitic material is more significant with increasing of copper amount and/or organic concentration in the starting solution. These increases lead to the affectation of apatite crystallinity. The IR spectroscopy shows the conservation of (Psbnd OH) band of (HPO4)2- groups, suggesting that PASP acid was interacted only with metallic cations of hydroxyapatite.

Sorption of uranyl ions from various acido systems by amphoteric epoxy amine ion-exchange resins

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

Rychkov, V.N.; Radionov, B.K.; Molochnikov, L.S.

1995-03-01

Sorption of uranyl ions by epoxy amine ampholytes with N-monomethylenephosphonic acid groups modified with pyridine or quaternary ammonium groups was studied under dynamic conditions. Heterocyclic nitrogen favors sorption of uranyl ion from fluoride, sulfate, and fluoride-sulfate solutions. The ESR studies of mono- and bimetallic forms of nitrogen-containing ampholytes with copper(II) as paramagnetic marker revealed the characteristics of uranium(VI) interaction with cation- and anion-exchange groups and its dependence on the fluoride content in solution.

Insights on the SO2 Poisoning of Pt3Co/VC and Pt/VC Fuel Cell Catalysts

DTIC Science & Technology

2010-01-01

catalyst is performed at the cathode of proton exchange membrane fuel cells ( PEMFCs ) in order to link previously reported results at the elec- trode...stripping voltammetry and underpotential deposition (upd) of copper adatoms. Then the performance of PEMFC cathodes employing 30wt.% Pt3Co/VC and 50wt.% Pt/VC...proton exchange membrane fuel cells( PEMFCs )in order to link previously reported results at the elec- trode/solution interface to the FC environment. First

Electronic computers and telephone exchanges

NASA Astrophysics Data System (ADS)

Flowers, T. H.

1980-01-01

A retrospective on the telephone, with emphasis on development of digital methods, is presented. Starting with its invention in 1876, major breakthroughs in transmission and switching circuitry are reviewed. The thermionic valve (1917), the Eccles-Jordan trigger circuit (1921), copper oxide rectifiers (1920's), and the gas-tube binary counter (1931) are highlighted. The evolution of logic design in telephone exchanges and the interaction this had with electronic computers is then traced up to the appearance of COLOSSUS, a specialized electronic computer used for cryptanalysis (1943).

Specific labeling of zinc finger proteins using noncanonical amino acids and copper-free click chemistry.

PubMed

Kim, Younghoon; Kim, Sung Hoon; Ferracane, Dean; Katzenellenbogen, John A; Schroeder, Charles M

2012-09-19

Zinc finger proteins (ZFPs) play a key role in transcriptional regulation and serve as invaluable tools for gene modification and genetic engineering. Development of efficient strategies for labeling metalloproteins such as ZFPs is essential for understanding and controlling biological processes. In this work, we engineered ZFPs containing cysteine-histidine (Cys2-His2) motifs by metabolic incorporation of the unnatural amino acid azidohomoalanine (AHA), followed by specific protein labeling via click chemistry. We show that cyclooctyne promoted [3 + 2] dipolar cycloaddition with azides, known as copper-free click chemistry, provides rapid and specific labeling of ZFPs at high yields as determined by mass spectrometry analysis. We observe that the DNA-binding activity of ZFPs labeled by conventional copper-mediated click chemistry was completely abolished, whereas ZFPs labeled by copper-free click chemistry retain their sequence-specific DNA-binding activity under native conditions, as determined by electrophoretic mobility shift assays, protein microarrays, and kinetic binding assays based on Förster resonance energy transfer (FRET). Our work provides a general framework to label metalloproteins such as ZFPs by metabolic incorporation of unnatural amino acids followed by copper-free click chemistry.

Specific Labeling of Zinc Finger Proteins using Non-canonical Amino Acids and Copper-free Click Chemistry

PubMed Central

Kim, Younghoon; Kim, Sung Hoon; Ferracane, Dean; Katzenellenbogen, John A.

2012-01-01

Zinc finger proteins (ZFPs) play a key role in transcriptional regulation and serve as invaluable tools for gene modification and genetic engineering. Development of efficient strategies for labeling metalloproteins such as ZFPs is essential for understanding and controlling biological processes. In this work, we engineered ZFPs containing cysteine-histidine (Cys2-His2) motifs by metabolic incorporation of the unnatural amino acid azidohomoalanine (AHA), followed by specific protein labeling via click chemistry. We show that cyclooctyne promoted [3 + 2] dipolar cycloaddition with azides, known as copper-free click chemistry, provides rapid and specific labeling of ZFPs at high yields as determined by mass spectrometry analysis. We observe that the DNA-binding activity of ZFPs labeled by conventional copper-mediated click chemistry was completely abolished, whereas ZFPs labeled by copper-free click chemistry retain their sequence-specific DNA-binding activity under native conditions, as determined by electrophoretic mobility shift assays, protein microarrays and kinetic binding assays based on Förster resonance energy transfer (FRET). Our work provides a general framework to label metalloproteins such as ZFPs by metabolic incorporation of unnatural amino acids followed by copper-free click chemistry. PMID:22871171

Improving wettability of photo-resistive film surface with plasma surface modification for coplanar copper pillar plating of IC substrates

NASA Astrophysics Data System (ADS)

Xiang, Jing; Wang, Chong; Chen, Yuanming; Wang, Shouxu; Hong, Yan; Zhang, Huaiwu; Gong, Lijun; He, Wei

2017-07-01

The wettability of the photo-resistive film (PF) surfaces undergoing different pretreatments including the O2sbnd CF4 low-pressure plasma (OCLP) and air plasma (AP), is investigated by water contact angle measurement instrument (WCAMI) before the bottom-up copper pillar plating. Chemical groups analysis performed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectra (XPS) shows that after the OCLP and wash treatment, the wettability of PF surface is attenuated, because embedded fluorine and decreased oxygen content both enhance hydrophobicity. Compared with OCLP treatment, the PF surface treatment by non-toxic air plasma displays features of Csbnd O, Osbnd Cdbnd O, Cdbnd O and sbnd NO2 by AIR-FTIR and XPS, and a promoted wettability by WCAM. Under the identical electroplating condition, the surface with a better wettability allows electrolyte to spontaneously soak all the places of vias, resulting in improved copper pillar uniformity. Statistical analysis of metallographic data shows that more coplanar and flat copper pillars are achieved with the PF treatment of air plasma. Such modified copper-pillar-plating technology meets the requirement of accurate impedance, the high density interconnection for IC substrates.

Sorption of lead ions on diatomite and manganese oxides modified diatomite.

PubMed

Al-Degs, Y; Khraisheh, M A; Tutunji, M F

2001-10-01

Naturally occurring diatomaceous earth (diatomite) has been tested as a potential sorbent for Pb(II) ions. The intrinsic exchange properties were further improved by modification with manganese oxides. Modified adsorbent (referred to as Mn-diatomite) showed a higher tendency for adsorbing lead ions from solution at pH 4. The high performance exhibited by Mn-diatomite was attributed to increased surface area and higher negative surface charge after modification. Scanning electron microscope pictures revealed a birnessite structure of manganese oxides, which was featured by a plate-like-crystal structure. Diatomite filtration quality was improved after modification by manganese oxides. Good filtration qualities combined with high exchange capacity emphasised the potential use of Mn-diatomite in filtration systems.

Temperature dependence of the effective interdimer exchange interaction in a weakly coupled antiferromagnetic dimer copper compound

NASA Astrophysics Data System (ADS)

Calvo, Rafael; Santana, Vinicius T.; Nascimento, Otaciro R.

2017-08-01

We report a variation with temperature T of the effective interdimeric interaction Jeff' in the antiferromagnetic (AFM) copper dimeric organic compound Cu2[TzTs] 4 (N -thiazol-2-yl-toluenesulfonamidate CuII). This T dependence was obtained from measurements of the effects in the electron paramagnetic resonance (EPR) spectra of the proposed quantum phase transition associated with the exchange-narrowing processes. Cu2[TzTs] 4 contains exchange-coupled pairs of CuII spins SA and SB (S =1 /2 ), with intradimeric AFM exchange coupling J0=(-115 ±1 ) cm-1 (Hex=-J0SA.SB ). The variation of the EPR linewidth of single crystals with field orientation around a "magic angle" where the transitions intersect and the integrated signal intensity of the so-called U peak of the powder spectrum were measured as a function of T . Modeling these data using arguments of exchange narrowing in the adiabatic regime considering the angular variation of the single-crystal spectra and a geometric description, we find that the effective interdimeric coupling | Jeff'| associated with the exchange frequency ωex is negligible for T ≪| J0/kB| when the units are uncoupled and | Jeff'|=(0.080 ±0.005 ) cm-1 (| Jeff'/J0|=7.0 × 10-4 ) at 298 K. Within this T interval, two ranges of | Jeff'| with linear temperature variation but different slopes, with a kink at ˜80 K, are observed and discussed. This T dependence arises from the growing population of the triplet state, and its relevance to the properties of various arrays of dimeric units is discussed. Our experimental procedures and results are compared with those of previous works in ion radical salts and dimeric metal compounds. The relation between the effective coupling | Jeff'| and the real interdimeric exchange coupling | J'| related to the chemical paths connecting neighbor units is discussed.

Reduction of liquid metal embrittlement in copper-brazed stainless steel joints

NASA Astrophysics Data System (ADS)

Uhlig, T.; Fedorov, V.; Elßner, M.; Wagner, G.; Weis, S.

2017-03-01

Due to its very good formability and the low raw material cost, pure copper in form of foils is commonly used to braze plate heat exchangers made of stainless steel. The difference in the electrochemical potentials of brazing filler and base material leads to corrosion effects in contact with electrolytes. This may lead to leakages, which decrease the reliability of the heat exchanger during service in potable water. The dissolution of the emerging corrosion products of brazing filler and base material induces the migration of heavy metal ions, such as Cu2+ and Ni2+, into the potable water. The so-called liquid metal embrittlement, which takes place during the brazing process, may intensify the corrosion. The brazing filler infiltrates the stainless steel along the grain boundaries and causes an embrittlement. This paper deals with the determination of the grain boundary erosion dependent on the degree of deformation and heat treatment of the stainless steel AISI 316L.

Relationship between organic matter humification and bioavailability of sludge-borne copper and cadmium during long-term sludge amendment to soil.

PubMed

Liu, Hongtao

2016-10-01

Recycling of sludge as soil amendment poses certain risk of heavy metals contamination. This study investigated the relationship between organic matter in composted sludge and its heavy metals bioavailability over 7years. Periodic monitoring indicated a gradual increase in organic matter degradation, accompanied by changing degrees of polymerization, i.e., ratio of humic acid (HA)/fulvic acid (FA) coupled with incremental exchangeable fraction of copper (Cu) in sludge, with a growing rate of 74.7%, rather than that in soil. However, cadmium (Cd) in composted sludge exhibited an independent manner. Linear-regression analysis revealed that the total proportion of the Cu active fraction (exchangeable plus carbonate bound) was better correlated with the degree of polymerization (DP) and humification ratio (HR) than the degradation ratio of organic matter. Overall, amount of uptaken Cu was more dependent on the humification degree of organic matter, especially the proportion of HA in humus. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption and mobility of metals in build-up on road surfaces.

PubMed

Gunawardana, Chandima; Egodawatta, Prasanna; Goonetilleke, Ashantha

2015-01-01

The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal. Copyright © 2014 Elsevier Ltd. All rights reserved.

Copper Modified Magnetic Bimetallic Nano-catalysts Ligand Regulated Catalytic Activity

EPA Science Inventory

Postsynthetic modification of magnetic nano ferrites (Fe3O4) has been accomplished by anchoring glutathione and dopamine on the surface. The Cu nano particles immobilized over these surfaces were investigated for the coupling and cyclo addition reactions. The Fe3O4-DOPA-Cu (na...

Symmetric and asymmetric exchange stiffnesses of transition-metal thin film interfaces in external electric field

NASA Astrophysics Data System (ADS)

Nakamura, K.; Pradipto, A.-M.; Akiyama, T.; Ito, T.; Oguchi, T.; Weinert, M.

2018-07-01

The electric-field induced modifications of the symmetric and asymmetric exchange stiffness constants for the prototypical transition-metal system of a Co monolayer on Pt(111) are determined from first-principles calculated total energy differences of spin-spiral states with oppositely rotating magnetizations in the presence of both the external field and spin-orbit coupling. The trend underlying the modifications is shown to be linked to orbital magnetism. The results demonstrate that an electric field may be a promising approach to manipulate macroscopically magnetic textures.

Flavonoids and urate antioxidant interplay in plasma oxidative stress.

PubMed

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

2001-05-01

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

Transfer Efficiency and Cooling Cost by Thermal Loss based on Nitrogen Evaporation Method for Superconducting MAGLEV System

NASA Astrophysics Data System (ADS)

Chung, Y. D.; Kim, D. W.; Lee, C. Y.

2017-07-01

This paper presents the feasibility of technical fusion between wireless power transfer (WPT) and superconducting technology to improve the transfer efficiency and evaluate operating costs such as refrigerant consumption. Generally, in WPT technology, the various copper wires have been adopted. From this reason, the transfer efficiency is limited since the copper wires of Q value are intrinsically critical point. On the other hand, as superconducting wires keep larger current density and relatively higher Q value, the superconducting resonance coil can be expected as a reasonable option to deliver large transfer power as well as improve the transfer ratio since it exchanges energy at a much higher rate and keeps stronger magnetic fields out. However, since superconducting wires should be cooled indispensably, the cooling cost of consumed refrigerant for resonance HTS wires should be estimated. In this study, the transmission ratios using HTS resonance receiver (Rx) coil and various cooled and noncooled copper resonance Rx coils were presented under non cooled copper antenna within input power of 200 W of 370 kHz respectively. In addition, authors evaluated cooling cost of liquid nitrogen for HTS resonance coil and various cooled copper resonance coils based on nitrogen evaporation method.

A novel assay method for the trace determination of Th and U in copper and lead using inductively coupled plasma mass spectrometry

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

LaFerriere, Brian D.; Maiti, Tapas C.; Arnquist, Isaac J.

2015-03-01

This study describes a novel sample preparation and assay method developed in support of the MAJORANA DEMONSTRATOR experiment for the determination of thorium and uranium levels in copper and lead shielding components. Meticulously clean sample preparation methods combined with novel anion exchange separations for analyte pre-concentration and matrix removal were developed. Quantification was performed by inductively coupled plasma mass spectrometry. Detection limits of 0.0084 pg 232Th/g and 0.0106 pg 238U/g were determined for copper, while detection limits of 0.23 pg 232Th/g and 0.46 pg 238U/g were achieved for lead. These methods allow the Majorana Collaboration to accurately assay detector componentsmore » and ensure that the experiment’s stringent radiopurity requirements are met.« less

DEVELOPMENT OF A REPRODUCIBLE SCREENING METHOD TO DETERMINE THE MECHANISM AND EFFECT OF ORGANIC ACIDS AND OTHER CONTAMINANTS ON THE CORROSION OF ALUMINUM-FINNED COPPER-TUBE HEAT EXCHANGE COILS

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

Richard A. Corbett; Dave Severance

2005-02-01

Formicary corrosion is an insidious form of localized pitting corrosion. Notoya (1997b) wrote, ?In Japan, this type of corrosion is found in approximately 10% of cases of premature failure of copper tubes.? Attack characteristically features very small surface pits which are not visible to the un-aided eye, and random directional changes in the underlying copper metal. Attack is rapid. Failures have occurred before installation, shortly thereafter, or within several years later. Objectives of this Research Project Conduct an in depth literature search on the subject of formicary corrosion. Define the corrosion mechanism. Develop a test method that will reproduce formicarymore » corrosion. Develop a test method for screening candidate materials that could cause formicary corrosion.« less

Effect of nanosecond UV laser irradiation on luminescence and absorption in silver- and copper-containing phosphate glasses

NASA Astrophysics Data System (ADS)

Murashov, A. A.; Sidorov, A. I.; Stoliarchuk, M. V.

2018-03-01

Experimental evidence is presented that nanosecond UV laser irradiation of silver- and copper-containing barium phosphate glasses leads to luminescence quenching in the visible range. Subsequent heat treatment induces an absorption in the range 350–500 nm. These effects are due to the ionisation and fragmentation of subnanometre molecular clusters by laser radiation and subsequent (heat treatment-induced) formation of nanoparticles possessing plasmon resonance. Our numerical modelling results demonstrate the feasibility of producing stable AgnCum hybrid molecular clusters in glass. Local modification of the optical properties of glass by laser light can be used for optical information recording.

REMOVAL OF COPPER-BASED CATALYST IN ATOM TRANSFER RADICAL POLYMERIZATION USING ION EXCHANGE RESINS. (R826735)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Integration of chemical and toxicological tools to assess the bioavailability of copper derived from different copper-based fungicides in soil.

PubMed

Wang, Quan-Ying; Sun, Jing-Yue; Xu, Xing-Jian; Yu, Hong-Wen

2018-06-20

Because the extensive use of Cu-based fungicides, the accumulation of Cu in agricultural soil has been widely reported. However, little information is known about the bioavailability of Cu deriving from different fungicides in soil. This paper investigated both the distribution behaviors of Cu from two commonly used fungicides (Bordeaux mixture and copper oxychloride) during the aging process and the toxicological effects of Cu on earthworms. Copper nitrate was selected as a comparison during the aging process. The distribution process of exogenous Cu into different soil fractions involved an initial rapid retention (the first 8 weeks) and a following slow continuous retention. Moreover, Cu mainly moved from exchangeable and carbonate fractions to Fe-Mn oxides-combined fraction during the aging process. The Elovich model fit well with the available Cu aging process, and the transformation rate was in the order of Cu(NO 3 ) 2 > Bordeaux mixture > copper oxychloride. On the other hand, the biological responses of earthworms showed that catalase activities and malondialdehyde contents of the copper oxychloride treated earthworms were significantly higher than those of Bordeaux mixture treated earthworms. Also, body Cu loads of earthworms from different Cu compounds spiked soils were in the following order: copper oxychloride > Bordeaux mixture. Thus, the bioavailability of Cu from copper oxychloride in soil was significantly higher than that of Bordeaux mixture, and different Cu compounds should be taken into consideration when studying the bioavailability of Cu-based fungicides in the soil. Copyright © 2018 Elsevier Inc. All rights reserved.

Cu2+ triggers reversible aggregation of a disordered His-rich dehydrin MpDhn12 from Musa paradisiaca.

PubMed

Mu, Peiqiang; Feng, Dongru; Su, Jianbin; Zhang, Yang; Dai, Jinran; Jin, Honglei; Liu, Bing; He, Yanming; Qi, Kangbiao; Wang, Hongbin; Wang, Jinfa

2011-11-01

Copper is an essential nutrient, but it is toxic in excess. Here, we cloned and characterized a His-rich low molecular weight dehydrin from Musa paradisiaca, MpDhn12. Analysis by circular dichroism (CD) spectra and a thermal stability assay showed that MpDhn12 is an intrinsically disordered protein, and immobilized-metal affinity chromatography (IMAC) analysis revealed that MpDhn12 can bind Cu(2+) both in vitro and in vivo. Interestingly, MpDhn12 aggregated under excess Cu(2+) conditions, and the aggregation was reversible and impaired by histidine modification with diethylpyrocarbonate (DEPC), while the disordered structure of another dehydrin ERD14 (as a control) was not changed. Furthermore, MpDhn12 could complement the copper-sensitive phenotype of yeast mutant Δsod1. These results together suggested that MpDhn12 may take part in buffering copper levels through chelation and formation of aggregates in excess Cu(2+) conditions. To the best of our knowledge, it is the first report that a dehydrin interchanged between disordered and aggregated state triggered by copper.

41 CFR 102-33.360 - What is the process for selling or exchanging aircraft parts for replacement?

Code of Federal Regulations, 2010 CFR

2010-07-01

... selling or exchanging aircraft parts for replacement? 102-33.360 Section 102-33.360 Public Contracts and... selling or exchanging aircraft parts for replacement? (a) You or your agent (e.g., another Federal agency... applicable labels and tags, historical data and modification records accompany the parts at the time of sale...

Electric-field-induced modification of the magnon energy, exchange interaction, and curie temperature of transition-metal thin films.

PubMed

Oba, M; Nakamura, K; Akiyama, T; Ito, T; Weinert, M; Freeman, A J

2015-03-13

The electric-field-induced modification in the Curie temperature of prototypical transition-metal thin films with the perpendicular magnetic easy axis, a freestanding Fe(001) monolayer and a Co monolayer on Pt(111), is investigated by first-principles calculations of spin-spiral structures in an external electric field (E field). An applied E field is found to modify the magnon (spin-spiral formation) energy; the change arises from the E-field-induced screening charge density in the spin-spiral states due to p-d hybridizations. The Heisenberg exchange parameters obtained from the magnon energy suggest an E-field-induced modification of the Curie temperature, which is demonstrated via Monte Carlo simulations that take the magnetocrystalline anisotropy into account.

Optimization of instantaneous solvent exchange/surface modification process for ambient synthesis of monolithic silica aerogels.

PubMed

Hwang, Sung-Woo; Kim, Tae-Youn; Hyun, Sang-Hoon

2008-06-01

The instantaneous solvent exchange/surface modification (ISE/SM) process for the ambient synthesis of crack-free silica aerogel monoliths with a high production yield was optimized. Monolithic forms of silica wet gels were obtained from aqueous colloidal silica sols prepared via the ion exchange of sodium silicate solutions. Crack-free silica aerogel monoliths were synthesized via an ISE/SM process using isopropyl alcohol/trimethylchlorosilane as a modification agent and n-hexane as a main solvent, followed by ambient drying. The optimum process conditions of the ISE/SM process were investigated by clarifying the reaction mechanism and phenomena. Most effective ranges of process variables on the ISE/SM stage were determined as 0.2500-0.3567 of TMCS/H2O (pore water) in molar ratio and 15-30 of n-hexane/TMCS in volumetric ratio, with a reaction temperature below 283 K. Crack-free silica aerogel monoliths synthesized via these conditions had a well-developed mesoporous structure and excellent properties (bulk density of 0.12-0.14 g/cm3, specific surface area of 724 m2/g), and a high yield (nearly 80%).

Alaska Department of Transportation and Public Facilities research and technology transfer peer exchange, July 31-August 4, 2006.

DOT National Transportation Integrated Search

2006-07-01

The objectives of the peer exchange were to explore: : -Project Selection: Models/modifications that might be considered : -Project Management: Highest value/best use of our two Research Engineers : -Research Implementation: Core Curriculum developme...

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

NASA Astrophysics Data System (ADS)

Kriegel, Ilka; Scotognella, Francesco; Manna, Liberato

2017-02-01

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

Energy saving incineration of waste

NASA Astrophysics Data System (ADS)

Meierzukoecker, H.; Voegtli, R.

1982-11-01

The machanism and the dimension of the preoxidation of the pollutants in the heat exchanger were investigated. A temperature control system was developed and tested. It is found that the preoxidation in the heat exchanger depends on the peculiarity of the pollutants and is inhibited by inactive walls with increasing of the specific surface. Active materials like copper only promote the oxidation of all pollutants in the low temperature region. Savings of supplemental energy about 25% are possible using process controlled auxiliary firing and combustion enthalpy of pollutants as a substitute for the supplemental energy.

Production Of High Specific Activity Copper-67

DOEpatents

Jamriska, Sr., David J.; Taylor, Wayne A.; Ott, Martin A.; Fowler, Malcolm; Heaton, Richard C.

2002-12-03

A process for the selective production and isolation of high specific activity cu.sup.67 from proton-irradiated enriched Zn.sup.70 target comprises target fabrication, target irradiation with low energy (<25 MeV) protons, chemical separation of the Cu.sup.67 product from the target material and radioactive impurities of gallium, cobalt, iron, and stable aluminum via electrochemical methods or ion exchange using both anion and cation organic ion exchangers, chemical recovery of the enriched Zn.sup.70 target material, and fabrication of new targets for re-irradiation is disclosed.

Production Of High Specific Activity Copper-67

DOEpatents

Jamriska, Sr., David J.; Taylor, Wayne A.; Ott, Martin A.; Fowler, Malcolm; Heaton, Richard C.

2003-10-28

A process for the selective production and isolation of high specific activity Cu.sup.67 from proton-irradiated enriched Zn.sup.70 target comprises target fabrication, target irradiation with low energy (<25 MeV) protons, chemical separation of the Cu.sup.67 product from the target material and radioactive impurities of gallium, cobalt, iron, and stable aluminum via electrochemical methods or ion exchange using both anion and cation organic ion exchangers, chemical recovery of the enriched Zn.sup.70 target material, and fabrication of new targets for re-irradiation is disclosed.

Mechanochemical Synthesis of Hydroxyapatite and Its Modifications: Composition, Structure, and Properties

NASA Astrophysics Data System (ADS)

Chaikina, M. V.; Bulina, N. V.; Ishchenko, A. V.; Prosanov, I. Yu.

2014-02-01

The mechanochemical method is used to synthesize samples of hydroxyapatite (HA) with substitution of the phosphate ion by silicate and zirconate ions, and substitution of calcium ions by copper ions. In the process of mechanochemical synthesis, carbonate ions and water molecules are incorporated into the structure of HA due to interaction of components of the reaction mixture with air. Intrusion of carbonate into the structure of HA is a competing process with modification of apatite by silicate and zirconate anions; therefore, the composition of the product during synthesis differs from the prescribed one. After annealing of the samples, the composition of the anion-modified HA can be described by the formula Са10(РО4)6- х (АО4) х (ОН)2- х , where (АО4)4- is the modifying anion. Substitution of calcium by copper ions localized at the Са1 position has been detected. Silver ions are not incorporated into the structure of HA, but are distributed in the apatite matrix in the form of nanocrystals of metallic silver.

Antimicrobial Properties of Selected Copper Alloys on Staphylococcus aureus and Escherichia coli in Different Simulations of Environmental Conditions: With vs. without Organic Contamination

PubMed Central

Różańska, Anna; Chmielarczyk, Agnieszka; Romaniszyn, Dorota; Sroka-Oleksiak, Agnieszka; Bulanda, Małgorzata; Walkowicz, Monika; Osuch, Piotr; Knych, Tadeusz

2017-01-01

Background: Hospital equipment made from copper alloys can play an important role in complementing traditional methods of disinfection. Aims of the study: The aim of this study was to assess the dynamics of the antimicrobial properties of selected copper alloys in different simulations of environmental conditions (with organic contamination vs. without organic contamination), and to test alternatives to the currently used testing methods. Materials and Methods: A modification of Japanese standard JIS Z 2801 as well as Staphylococcus aureus (SA) and Escherichia coli (EC) suspended in NaCl vs. tryptic soy broth (TSB) were used in tests performed on seven commonly used copper alloys, copper, and stainless steel. Results: A much faster reduction of the bacterial suspension was observed for the inoculum prepared in NaCl than in TSB. A faster reduction for EC than for SA was observed in the inoculum prepared in NaCl. The opposite results were found for the inoculum based on TSB. A significant correlation between the copper concentration in the copper alloys and the time and degree of bacterial suspension reduction was only observed in the case of EC. Conclusions: This study confirmed the antimicrobial properties of copper alloys, and additionally showed that Staphylococcus aureus was more resistant than Escherichia coli in the variant of the experiment without organic contamination. However, even for SA, a total reduction of the bacterial inoculum’s density took no longer than 2 h. Under conditions simulating organic contamination, all of the tested alloys were shown to have bactericidal or bacteriostatic properties, which was contrary to the results from stainless steel. PMID:28726753

Antimicrobial Properties of Selected Copper Alloys on Staphylococcus aureus and Escherichia coli in Different Simulations of Environmental Conditions: With vs. without Organic Contamination.

PubMed

Różańska, Anna; Chmielarczyk, Agnieszka; Romaniszyn, Dorota; Sroka-Oleksiak, Agnieszka; Bulanda, Małgorzata; Walkowicz, Monika; Osuch, Piotr; Knych, Tadeusz

2017-07-20

Background: Hospital equipment made from copper alloys can play an important role in complementing traditional methods of disinfection. Aims of the study: The aim of this study was to assess the dynamics of the antimicrobial properties of selected copper alloys in different simulations of environmental conditions (with organic contamination vs. without organic contamination), and to test alternatives to the currently used testing methods. Materials and Methods: A modification of Japanese standard JIS Z 2801 as well as Staphylococcus aureus (SA) and Escherichia coli (EC) suspended in NaCl vs. tryptic soy broth (TSB) were used in tests performed on seven commonly used copper alloys, copper, and stainless steel. Results: A much faster reduction of the bacterial suspension was observed for the inoculum prepared in NaCl than in TSB. A faster reduction for EC than for SA was observed in the inoculum prepared in NaCl. The opposite results were found for the inoculum based on TSB. A significant correlation between the copper concentration in the copper alloys and the time and degree of bacterial suspension reduction was only observed in the case of EC. Conclusions: This study confirmed the antimicrobial properties of copper alloys, and additionally showed that Staphylococcus aureus was more resistant than Escherichia coli in the variant of the experiment without organic contamination. However, even for SA, a total reduction of the bacterial inoculum's density took no longer than 2 h. Under conditions simulating organic contamination, all of the tested alloys were shown to have bactericidal or bacteriostatic properties, which was contrary to the results from stainless steel.

Position-dependent performance of copper phthalocyanine based field-effect transistors by gold nanoparticles modification.

PubMed

Luo, Xiao; Li, Yao; Lv, Wenli; Zhao, Feiyu; Sun, Lei; Peng, Yingquan; Wen, Zhanwei; Zhong, Junkang; Zhang, Jianping

2015-01-21

A facile fabrication and characteristics of copper phthalocyanine (CuPc)-based organic field-effect transistor (OFET) using the gold nanoparticles (Au NPs) modification is reported, thereby achieving highly improved performance. The effect of Au NPs located at three different positions, that is, at the SiO2/CuPc interface (device B), embedding in the middle of CuPc layer (device C), and on the top of CuPc layer (device D), is investigated, and the results show that device D has the best performance. Compared with the device without Au NPs (reference device A), device D displays an improvement of field-effect mobility (μ(sat)) from 1.65 × 10(-3) to 5.51 × 10(-3) cm(2) V(-1) s(-1), and threshold voltage decreases from -23.24 to -16.12 V. Therefore, a strategy for the performance improvement of the CuPc-based OFET with large field-effect mobility and saturation drain current is developed, on the basis of the concept of nanoscale Au modification. The model of an additional electron transport channel formation by FET operation at the Au NPs/CuPc interface is therefore proposed to explain the observed performance improvement. Optimum CuPc thickness is confirmed to be about 50 nm in the present study. The device-to-device uniformity and time stability are discussed for future application.

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

PubMed

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

2009-09-22

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

Thermal emittance enhancement of graphite-copper composites for high temperature space based radiators

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Forkapa, Mark J.; Cooper, Jill M.

1991-01-01

Graphite-copper composites are candidate materials for space based radiators. The thermal emittance of this material, however, is a factor of two lower than the desired emittance for these systems of greater than or equal to 0.85. Arc texturing was investigated as a surface modification technique for enhancing the emittance of the composite. Since the outer surface of the composite is copper, and samples of the composite could not be readily obtained for testing, copper was used for optimization testing. Samples were exposed to various frequencies and currents of arcs during texturing. Emittances near the desired goal were achieved at frequencies less than 500 Hz. Arc current did not appear to play a major role under 15 amps. Particulate carbon was observed on the surface, and was easily removed by vibration and handling. In order to determine morphology adherence, ultrasonic cleaning was used to remove the loosely adherent material. This reduced the emittance significantly. Emittance was found to increase with increasing frequency for the cleaned samples up to 500 Hz. The highest emittance achieved on these samples over the temperature range of interest was 0.5 to 0.6, which is approximately a factor of 25 increase over the untextured copper emittance.

New highlights on degradation process of verdigris from easel paintings

NASA Astrophysics Data System (ADS)

Santoro, Carlotta; Zarkout, Karim; Le Hô, Anne-Solenn; Mirambet, François; Gourier, Didier; Binet, Laurent; Pagès-Camagna, Sandrine; Reguer, Solenn; Mirabaud, Sigrid; Le Du, Yann; Griesmar, Pascal; Lubin-Germain, Nadège; Menu, Michel

2014-03-01

Verdigris is a green copper organometallic pigment, widely used in paintings during the fifteenth and sixteenth centuries. With ageing, chromatic modifications like browning or darkening can be observed on those green painted layers. An original but crucial approach has been developed based on the characterization of a reference neutral verdigris pigment—anhydrous copper acetate—and model samples, made of verdigris and linseed oil. Samples have undergone artificial ageing (temperature, light) to reproduce the color change effect. They were analysed before and after accelerated ageing tests by a complementary set of classical techniques: colorimetry, electron paramagnetic resonance, X-ray absorption spectroscopy, and UV-visible absorption. Our experiments revealed that the incorporation of the verdigris pigment in linseed oil induces a transformation of the copper acetate bimetallic structure, with the formation of monomeric species. These monomers, however, are not directly responsible for the darkening. The chromatic alteration seems instead linked to the transient formation of Cu(I) in the copper complexes of the pigment/oil system. This formation could be initiated by ambient light absorption through ligand-to-metal charge transfer, which favors the decarboxylation of the copper complexes leading to the reduction of Cu(II) into Cu(I). Moreover, dioxygen can react with partially decarboxylated dimers to form peroxy-Cu dimer complexes that can be responsible for the darkening.

Lead and cadmium sorption mechanisms on magnetically modified biochars.

PubMed

Trakal, Lukáš; Veselská, Veronika; Šafařík, Ivo; Vítková, Martina; Číhalová, Sylva; Komárek, Michael

2016-03-01

This paper discusses Cd(II) and Pb(II) sorption efficiency of biochars modified by impregnation with magnetic particles. All selected biochar characteristics were significantly affected after the modification. More specifically, the cation exchange capacity increased after the modification, except for grape stalk biochar. However, the changes in the pH value, PZC, and BET surface after modification process were less pronounced. The metal loading rate was also significantly improved, especially for Cd(II) sorption on/in nut shield and plum stone biochars (10- and 16-times increase, respectively). The results indicated that cation exchange (as a metal sorption mechanism) was strengthened after Fe oxide impregnation, which limited the desorbed amount of tested metals. In contrast, the magnetization of grape stalk biochar reduced Pb(II) sorption in comparison with that of pristine biochar. Magnetic modification is, therefore, more efficient for biochars with well-developed structure and for more mobile metals, such as Cd(II). Copyright © 2015 Elsevier Ltd. All rights reserved.

Electric-field-induced modification in Curie temperature of Co monolayer on Pt(111)

NASA Astrophysics Data System (ADS)

Nakamura, Kohji; Oba, Mikito; Akiyama, Toru; Ito, Tomonori; Weinert, Michael

2015-03-01

Magnetism induced by an external electric field (E-field) has received much attention as a potential approach for controlling magnetism at the nano-scale with the promise of ultra-low energy power consumption. Here, the E-field-induced modification of the Curie temperature for a prototypical transition-metal thin layer of a Co monolayer on Pt(111) is investigated by first-principles calculations by using the full-potential linearized augmented plane wave method that treats spin-spiral structures in an E-field. An applied E-field modifies the magnon (spin-spiral formation) energies by a few meV, which leads to a modification of the exchange pair interaction parameters within the classical Heisenberg model. With inclusion of the spin-orbit coupling (SOC), the magnetocrystalline anisotropy and the Dzyaloshinskii-Morita interaction are obtained by the second variation SOC method. An E-field-induced modification of the Curie temperature is demonstrated by Monte Carlo simulations, in which a change in the exchange interaction is found to play a key role.

Weld Repair of Thin Aluminum Sheet

NASA Technical Reports Server (NTRS)

Beuyukian, C. S.; Mitchell, M. J.

1986-01-01

Weld repairing of thin aluminum sheets now possible, using niobium shield and copper heat sinks. Refractory niobium shield protects aluminum adjacent to hole, while copper heat sinks help conduct heat away from repair site. Technique limits tungsten/inert-gas (TIG) welding bombardment zone to melt area, leaving surrounding areas around weld unaffected. Used successfully to repair aluminum cold plates on Space Shuttle, Commercial applications, especially in sealing fractures, dents, and holes in thin aluminum face sheets or clad brazing sheet in cold plates, heat exchangers, coolers, and Solar panels. While particularly suited to thin aluminum sheet, this process also used in thicker aluminum material to prevent surface damage near weld area.

GRCop-84: A High Temperature Copper-based Alloy For High Heat Flux Applications

NASA Technical Reports Server (NTRS)

Ellis, David L.

2005-01-01

While designed for rocket engine main combustion chamber liners, GRCop-84 (Cu-8 at.% Cr-4 at.% Nb) offers potential for high heat flux applications in industrial applications requiring a temperature capability up to approximately 700 C (1292 F). GRCop-84 is a copper-based alloy with excellent elevated temperature strength, good creep resistance, long LCF lives and enhanced oxidation resistance. It also has a lower thermal expansion than copper and many other low alloy copper-based alloys. GRCop-84 can be manufactured into a variety of shapes such as tubing, bar, plate and sheet using standard production techniques and requires no special production techniques. GRCop-84 forms well, so conventional fabrication methods including stamping and bending can be used. GRCop-84 has demonstrated an ability to be friction stir welded, brazed, inertia welded, diffusion bonded and electron beam welded for joining to itself and other materials. Potential applications include plastic injection molds, resistance welding electrodes and holders, permanent metal casting molds, vacuum plasma spray nozzles and high temperature heat exchanger applications.

Effective removal of coordinated copper from wastewater using a new dithiocarbamate-type supramolecular heavy metal precipitant.

PubMed

Fu, Fenglian; Zeng, Haiyan; Cai, Qinhong; Qiu, Rongliang; Yu, Jimmy; Xiong, Ya

2007-11-01

A new dithiocarbamate-type heavy metal precipitant, sodium 1,3,5-hexahydrotriazinedithiocarbamate (HTDC), was prepared and used to remove coordinated copper from wastewater. In the reported dithiocarbamate-type precipitants, HTDC possesses the highest percentage of the effective functional groups. It could effectively precipitate copper to less than 0.5mgl(-1) from both synthetic and actual industrial wastewater containing CuEDTA in the range of pH 3-9. UV-vis spectral investigation and elemental analysis suggested that the precipitate was a kind of coordination supramolecular compound, [Cu(3)(HTDC)(2)](n). The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) indicated that the supramolecular precipitate was non-hazardous and stable in weak acid and alkaline conditions. Tests of an anion exchange resin D231 provided a clue to simultaneously remove excess HTDC and residual CuEDTA in practical process of wastewater treatment.

Copper stress on photosynthesis of black mangle (Avicennia germinans).

PubMed

González-Mendoza, Daniel; Espadas y Gil, Francisco; Escoboza-Garcia, Fernando; Santamaría, Jorge M; Zapata-Perez, Omar

2013-01-01

The effects of copper toxicity on the photosynthetic activities of Avicennia germinans was investigated using two CuSO4 concentrations (0.062 and 0.33 M) added in Hoagland's solution in an aerated hydroponic system. Photosynthesis and chlorophyll fluorescence were measured after 30 h of copper stress. Results obtained in this study show that increasing levels of Cu(+2) of 0.062 and 0.33 M Cu(+2) resulted in a general reduction of the stomatal conductance (28 and 18%, respectively) and 100% of inhibition of net photosynthesis. Additionally, at these concentrations of Cu(+2), reductions of chlorophyll fluorescence parameters were also observed. These changes suggested that the photosynthetic apparatus of Avicennia germinans was the primary target of the Cu(+2) action. It is concluded that Cu(+2) ions causes a drastic decline in photosynthetic gas exchange and Chlorophyll fluorescence parameters in A. germinans leaves.

Silicon Sheet Growth Development for the Large Area Sheet Task of the Low Cost Solar Array Project. Heat Exchanger Method - Ingot Casting Fixed Abrasive Method - Multi-Wire Slicing

NASA Technical Reports Server (NTRS)

Schmid, F.; Khattak, C. P.

1978-01-01

Solar cells fabricated from HEM cast silicon yielded up to 15% conversion efficiencies. This was achieved in spite of using unpurified graphite parts in the HEM furnace and without optimization of material or cell processing parameters. Molybdenum retainers prevented SiC formation and reduced carbon content by 50%. The oxygen content of vacuum cast HEM silicon is lower than typical Czochralski grown silicon. Impregnation of 45 micrometers diamonds into 7.5 micrometers copper sheath showed distortion of the copper layer. However, 12.5 micrometers and 15 micrometers copper sheath can be impregnated with 45 micrometers diamonds to a high concentration. Electroless nickel plating of wires impregnated only in the cutting edge showed nickel concentration around the diamonds. This has the possibility of reducing kerf. The high speed slicer fabricated can achieve higher speed and longer stroke with vibration isolation.

Flower-Like CuO/ZnO Hybrid Hierarchical Nanostructures Grown on Copper Substrate: Glycothermal Synthesis, Characterization, Hydrophobic and Anticorrosion Properties

PubMed Central

Beshkar, Farshad; Khojasteh, Hossein; Salavati-Niasari, Masoud

2017-01-01

In this work we have demonstrated a facile formation of CuO nanostructures on copper substrates by the oxidation of copper foil in ethylene glycol (EG) at 80 °C. On immersing a prepared CuO film into a solution containing 0.1 g Zn(acac)2 in 20 mL EG for 8 h, ZnO flower-like microstructures composed of hierarchical three-dimensional (3D) aggregated nanoparticles and spherical architectures were spontaneously formed at 100 °C. The as-synthesized thin films and 3D microstructures were characterized using XRD, SEM, and EDS techniques. The effects of sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), and polyethylene glycol (PEG) 6000 as surfactants and stabilizers on the morphology of the CuO and ZnO structures were discussed. Possible growth mechanisms for the controlled organization of primary building units into CuO nanostructures and 3D flower-like ZnO architectures were proposed. The hydrophobic property of the products was characterized by means of water contact angle measurement. After simple surface modification with stearic acid and PDMS, the resulting films showed hydrophobic and even superhydrophobic characteristics due to their special surface energy and nano-microstructure morphology. Importantly, stable superhydrophobicity with a contact angle of 153.5° was successfully observed for CuO-ZnO microflowers after modification with PDMS. The electrochemical impedance measurements proved that the anticorrosion efficiency for the CuO/ZnO/PDMS sample was about 99%. PMID:28773056

Flower-Like CuO/ZnO Hybrid Hierarchical Nanostructures Grown on Copper Substrate: Glycothermal Synthesis, Characterization, Hydrophobic and Anticorrosion Properties.

PubMed

Beshkar, Farshad; Khojasteh, Hossein; Salavati-Niasari, Masoud

2017-06-25

In this work we have demonstrated a facile formation of CuO nanostructures on copper substrates by the oxidation of copper foil in ethylene glycol (EG) at 80 °C. On immersing a prepared CuO film into a solution containing 0.1 g Zn(acac)₂ in 20 mL EG for 8 h, ZnO flower-like microstructures composed of hierarchical three-dimensional (3D) aggregated nanoparticles and spherical architectures were spontaneously formed at 100 °C. The as-synthesized thin films and 3D microstructures were characterized using XRD, SEM, and EDS techniques. The effects of sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), and polyethylene glycol (PEG) 6000 as surfactants and stabilizers on the morphology of the CuO and ZnO structures were discussed. Possible growth mechanisms for the controlled organization of primary building units into CuO nanostructures and 3D flower-like ZnO architectures were proposed. The hydrophobic property of the products was characterized by means of water contact angle measurement. After simple surface modification with stearic acid and PDMS, the resulting films showed hydrophobic and even superhydrophobic characteristics due to their special surface energy and nano-microstructure morphology. Importantly, stable superhydrophobicity with a contact angle of 153.5° was successfully observed for CuO-ZnO microflowers after modification with PDMS. The electrochemical impedance measurements proved that the anticorrosion efficiency for the CuO/ZnO/PDMS sample was about 99%.

Effect of market factors on the short-time pricing of stock-exchange metals

NASA Astrophysics Data System (ADS)

Bogdanov, S. V.; Shevelev, I. M.; Chernyi, S. A.

2016-12-01

The open trade on the world market is estimated using information of one-day exchange prices of nonferrous and precious metals, oil, reduced crude, and gasoline and the main world stock indices in the time period from January 1, 2009 to December 31, 2015. It is found that the short-term changes in the prices of nonferrous metals are determined by the prices on the metal market. The changes in the prices of energy carriers and the stock trade on the stock market weakly influence the pricing of nonferrous and precious metals. The prices of metals depend on the situation during trade on commodity exchanges, and the stock market indirectly influences the exchange prices of metals through changes in the share prices of the companies that produce copper, aluminum, and zinc.

76 FR 51878 - Modifications of Certain Derivative Contracts; Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-19

... Modifications of Certain Derivative Contracts; Correction AGENCY: Internal Revenue Service (IRS), Treasury... derivative contracts does not result in an exchange to the nonassigning counterparty for purposes of Sec. 1... derivative contract to another dealer in securities or'' is corrected to read ``or a clearinghouse transfers...

Effect of bentonite modification on hardness and mechanical properties of natural rubber nanocomposites

NASA Astrophysics Data System (ADS)

Santiago, Denise Ester O.; Pajarito, Bryan B.; Mangaccat, Winna Faye F.; Tigue, Maelyn Rose M.; Tipton, Monica T.

2016-05-01

The effect of sodium activation, ion-exchange with tertiary amine salt, surface treatment with non-ionic surfactant, and wet grinding of bentonite on hardness and mechanical properties of natural rubber nanocomposites (NRN) was studied using full factorial design of experiment. Results of X-ray diffraction (XRD) show increase in basal spacing d of bentonite due to modification, while attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirm the organic modification of bentonite. Analysis of variance (ANOVA) shows that the main effect of surface treatment increases the hardness and decreases the tensile modulus of the NRN. The surface treatment and wet grinding of bentonite decrease the tensile stresses at 100, 200 and 300% strain of NRN. Sodium activation and ion-exchange negatively affect the compressive properties, while surface treatment significantly improves the compressive properties of NRN.

Comparative study on the copper activation and xanthate adsorption on sphalerite and marmatite surfaces

NASA Astrophysics Data System (ADS)

Liu, Jian; Wang, Yu; Luo, Deqiang; Chen, Luzheng; Deng, Jiushuai

2018-05-01

The copper activation and potassium butyl xanthate (PBX) adsorption on sphalerite and marmatite surfaces were comparatively investigated using in situ local electrochemical impedance spectroscopy (LEIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and surface adsorption tests. Comparing the LEIS and surface adsorption results, it was found that the activation time is a key factor influencing the copper activation and PBX adsorption on marmatite surface, but it has a negligible influence on sphalerite. For a short activation time within 10 min, the Fe impurity in marmatite shows an adverse influence on the speed of Cu adsorption and ion exchange as well as on the subsequent PBX adsorption. For a long activation time of 30 min, the LEIS, ToF-SIMS and surface adsorption results suggested that the Fe impurity in marmatite enhances the copper adsorption, whereas such enhanced copper adsorption of marmatite cannot result in corresponding enhancing of PBX adsorption. DFT result showed that the Fe impurity in marmatite has harmful influence on the PBX interaction with the Cu-activated surface by increasing the interaction energy. ToF-SIMS result further indicated that the Cu distribution in the outermost surface of marmatite is less than that of the sphalerite, which also results in the less PBX adsorption for the marmatite.

XAFS study of copper and silver nanoparticles in glazes of medieval middle-east lustreware (10th-13th century)

NASA Astrophysics Data System (ADS)

Padovani, S.; Puzzovio, D.; Sada, C.; Mazzoldi, P.; Borgia, I.; Sgamellotti, A.; Brunetti, B. G.; Cartechini, L.; D'Acapito, F.; Maurizio, C.; Shokoui, F.; Oliaiy, P.; Rahighi, J.; Lamehi-Rachti, M.; Pantos, E.

2006-06-01

It has recently been shown that lustre decoration of medieval and Renaissance pottery consists of silver and copper nanoparticles dispersed in the glassy matrix of the ceramic glaze. Here the findings of an X-ray absorption fine structure (XAFS) study on lustred glazes of shards belonging to 10th and 13rd century pottery from the National Museum of Iran are reported. Absorption spectra in the visible range have been also measured in order to investigate the relations between colour and glaze composition. Gold colour is mainly due to Ag nanoparticles, though Ag+, Cu+ and Cu2+ ions can be also dispersed within the glassy matrix, with different ratios. Red colour is mainly due to Cu nanoparticles, although some Ag nanoparticles, Ag+ and Cu+ ions can be present. The achievement of metallic Cu and the absence of Cu2+ indicate a higher reduction of copper in red lustre. These findings are in substantial agreement with previous results on Italian Renaissance pottery. In spite of the large heterogeneity of cases, the presence of copper and silver ions in the glaze confirms that lustre formation is mediated by a copper- and silver-alkali ion exchange, followed by nucleation and growth of metal nanoparticles.

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

PubMed Central

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

2014-01-01

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

Thermoelectric Properties of Hot-Pressed and PECS-Sintered Magnesium-Doped Copper Aluminum Oxide

NASA Astrophysics Data System (ADS)

Liu, Chang; Morelli, Donald T.

2011-05-01

Copper aluminum oxide (CuAlO2) is considered as a potential candidate for thermoelectric applications. Partially magnesium-doped CuAlO2 bulk pellets were fabricated using solid-state reactions, hot-pressing, and pulsed electric current sintering (PECS) techniques. X-ray diffraction and scanning electron microscopy were adopted for structural analysis. High-temperature transport property measurements were performed on hot-pressed samples. Electrical conductivity increased with Mg doping before secondary phases became significant, while the Seebeck coefficient displayed the opposite trend. Thermal conductivity was consistently reduced as the Mg concentration increased. Effects of Mg doping, preparation conditions, and future modification on this material's properties are discussed.

Effect of ionizing radiation on structural and conductive properties of copper nanotubes

NASA Astrophysics Data System (ADS)

Zdorovets, M. V.; Borgekov, D. B.; Kenzhina, I. E.; Kozlovskiy, A. L.

2018-01-01

The use of electron radiation is an effective tool for stimulating a controlled modification of structural and conductive properties of nanomaterials in modern materials science. The paper presents the results of studies of the influence of various types of radiation on structural and conductive properties of copper nanotubes obtained by electrochemical synthesis in pores of templates based on polyethylene terephthalate. Such methods as SEM, X-ray diffraction and EDS show that irradiation with a stream of high-energy electrons with doses of 50-250 kGy makes it possible to modify the crystal structure of nanotubes, increasing their conductivity and decreasing the resistance of nanostructures without destroying the structure.

Hemoglobin and Myoglobin as Reducing Agents in Biological Systems. Redox Reactions of Globins with Copper and Iron Salts and Complexes.

PubMed

Postnikova, G B; Shekhovtsova, E A

2016-12-01

In addition to reversible O2 binding, respiratory proteins of the globin family, hemoglobin (Hb) and myoglobin (Mb), participate in redox reactions with various metal complexes, including biologically significant ones, such as those of copper and iron. HbO 2 and MbO 2 are present in cells in large amounts and, as redox agents, can contribute to maintaining cell redox state and resisting oxidative stress. Divalent copper complexes with high redox potentials (E 0 , 200-600 mV) and high stability constants, such as [Cu(phen) 2 ] 2+ , [Cu(dmphen) 2 ] 2+ , and CuDTA oxidize ferrous heme proteins by the simple outer-sphere electron transfer mechanism through overlapping π-orbitals of the heme and the copper complex. Weaker oxidants, such as Cu2+, CuEDTA, CuNTA, CuCit, CuATP, and CuHis (E 0 ≤ 100-150 mV) react with HbO 2 and MbO 2 through preliminary binding to the protein with substitution of the metal ligands with protein groups and subsequent intramolecular electron transfer in the complex (the site-specific outer-sphere electron transfer mechanism). Oxidation of HbO 2 and MbO 2 by potassium ferricyanide and Fe(3) complexes with NTA, EDTA, CDTA, ATP, 2,3-DPG, citrate, and pyrophosphate PP i proceeds mainly through the simple outer-sphere electron transfer mechanism via the exposed heme edge. According to Marcus theory, the rate of this reaction correlates with the difference in redox potentials of the reagents and their self-exchange rates. For charged reagents, the reaction may be preceded by their nonspecific binding to the protein due to electrostatic interactions. The reactions of LbO 2 with carboxylate Fe complexes, unlike its reactions with ferricyanide, occur via the site-specific outer-sphere electron transfer mechanism, even though the same reagents oxidize structurally similar MbO 2 and cytochrome b 5 via the simple outer-sphere electron transfer mechanism. Of particular biological interest is HbO 2 and MbO 2 transformation into met-forms in the presence of small amounts of metal ions or complexes (catalysis), which, until recently, had been demonstrated only for copper compounds with intermediate redox potentials. The main contribution to the reaction rate comes from copper binding to the "inner" histidines, His97 (0.66 nm from the heme) that forms a hydrogen bond with the heme propionate COO - group, and the distal His64. The affinity of both histidines for copper is much lower than that of the surface histidines residues, and they are inaccessible for modification with chemical reagents. However, it was found recently that the high-potential Fe(3) complex, potassium ferricyanide (400 mV), at a 5 to 20% of molar protein concentration can be an efficient catalyst of MbO 2 oxidation into metMb. The catalytic process includes binding of ferrocyanide anion in the region of the His119 residue due to the presence there of a large positive local electrostatic potential and existence of a "pocket" formed by Lys16, Ala19, Asp20, and Arg118 that is sufficient to accommodate [Fe(CN) 6 ] 4- . Fast, proton-assisted reoxidation of the bound ferrocyanide by oxygen (which is required for completion of the catalytic cycle), unlike slow [Fe(CN) 6 ] 4- oxidation in solution, is provided by the optimal location of neighboring protonated His113 and His116, as it occurs in the enzyme active site.

Biosorption of copper ions from dilute aqueous solutions on base treated rubber (Hevea brasiliensis) leaves powder: kinetics, isotherm, and biosorption mechanisms.

PubMed

Wan Ngah, W S; Hanafiah, M A K M

2008-01-01

The efficiency of sodium hydroxide treated rubber (Hevea brasiliensis) leaves powder (NHBL) for removing copper ions from aqueous solutions has been investigated. The effects of physicochemical parameters on biosorption capacities such as stirring speed, pH, biosorbent dose, initial concentrations of copper, and ionic strength were studied. The biosorption capacities of NHBL increased with increase in pH, stirring speed and copper concentration but decreased with increase in biosorbent dose and ionic strength. The isotherm study indicated that NHBL fitted well with Langmuir model compared to Freundlich and Dubinin-Radushkevich models. The maximum biosorption capacity determined from Langmuir isotherm was 14.97 mg/g at 27 degrees C. The kinetic study revealed that pseudosecond order model fitted well the kinetic data, while Boyd kinetic model indicated that film diffusion was the main rate determining step in biosorption process. Based on surface area analysis, NHBL has low surface area and categorized as macroporous. Fourier transform infrared (FT-IR) analyses revealed that hydroxyl, carboxyl, and amino are the main functional groups involved in the binding of copper ions. Complexation was one of the main mechanisms for the removal of copper ions as indicated by FT-IR spectra. Ion exchange was another possible mechanism since the ratio of adsorbed cations (Cu2+ and H+) to the released cations (Na+, Ca2+, and Mg2+) from NHBL was almost unity. Copper ions bound on NHBL were able to be desorbed at > 99% using 0.05 mol/L HCl, 0.01 mol/L HNO3, and 0.01 mol/L EDTA solutions.

31 CFR 100.11 - Exchange of bent and partial coins.

Code of Federal Regulations, 2013 CFR

2013-07-01

... partial coins shall be presented separately by denomination category in lots of at least one pound for... redeemed at the face value equivalent of copper one cent coins. (c) Redemption site. Bent and partial coins will be redeemed only at the United States Mint, P.O. Box 400, Philadelphia, PA 19105. Coins are...

China’s Assistance and Government-Sponsored Investment Activities in Africa, Latin America, and Southeast Asia

DTIC Science & Technology

2009-11-25

line.55 In January 2008, the Indonesian state electricity company signed an agreement with China’s Eximbank to borrow $615 million to build coal -fired...aid in the construction of infrastructure and educational facilities in exchange for rights over copper and cobalt deposits .37 Examples of PRC

75 FR 54199 - Self-Regulatory Organizations; NYSE Arca, Inc.; Notice of Filing of a Proposed Rule Change...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-03

... Commission has approved other exchange-traded fund- like products linked to the performance of underlying... (each, an ``Index Commodity'' and, collectively, ``Index Commodities''): Aluminum, cocoa, coffee, copper... products; Group II includes seven Index Commodities which are highly liquid; Group III is comprised of four...

40 CFR 142.62 - Variances and exemptions from the maximum contaminant levels for organic and inorganic chemicals.

Code of Federal Regulations, 2011 CFR

2011-07-01

... be required to convert Arsenic III to Arsenic V. 5 To obtain high removals, iron to arsenic ratio... Exchange 6=Lime Softening (not BAT for systems Corrosion... corrosion control treatment requirements for lead and copper in §§ 141.81 and 141.82 to avoid an...

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

Expanding the genetic code for site-specific labelling of tobacco mosaic virus coat protein and building biotin-functionalized virus-like particles.

PubMed

Wu, F C; Zhang, H; Zhou, Q; Wu, M; Ballard, Z; Tian, Y; Wang, J Y; Niu, Z W; Huang, Y

2014-04-18

A method for site-specific and high yield modification of tobacco mosaic virus coat protein (TMVCP) utilizing a genetic code expanding technology and copper free cycloaddition reaction has been established, and biotin-functionalized virus-like particles were built by the self-assembly of the protein monomers.

An orthogonal ferromagnetically coupled tetracopper(II) 2 x 2 homoleptic grid supported by micro-O4 bridges and its DFT study.

PubMed

Roy, Somnath; Mandal, Tarak Nath; Barik, Anil Kumar; Pal, Sachindranath; Butcher, Ray J; El Fallah, Mohamed Salah; Tercero, Javier; Kar, Susanta Kumar

2007-03-28

A pyrazole based ditopic ligand (PzOAP), prepared by the reaction between 5-methylpyrazole-3-carbohydrazide and methyl ester of imino picolinic acid, reacts with Cu(NO3)2.6H2O to form a self-assembled, ferromagnetically coupled, alkoxide bridged tetranuclear homoleptic Cu(II) square grid-complex [Cu4(PzOAP)4(NO3)2] (NO3)2.4H2O (1) with a central Cu4[micro-O4] core, involving four ligand molecules. In the Cu4[micro-O4] core, out of four copper centers, two copper centers are penta-coordinated and the remaining two are hexa-coordinated. In each case of hexa-coordination, the sixth position is occupied by the nitrate ion. The complex 1 has been characterized structurally and magnetically. Although Cu-O-Cu bridge angles are too large (138-141 degrees) and Cu-Cu distances are short (4.043-4.131 A), suitable for propagation of expected antiferromagnetic exchange interactions within the grid, yet intramolecular ferromagnetic exchange (J = 5.38 cm(-1)) is present with S = 4/2 magnetic ground state. This ferromagnetic interaction is quite obvious from the bridging connections (d(x2-y2)) lying almost orthogonally between the metal centers. The exchange pathways parameters have been evaluated from density functional calculations.

Numerical and experimental investigation of bi-annulus heat exchanger for different alternative materials

NASA Astrophysics Data System (ADS)

Zeeshan, M.; Duggal, R.; Tated, M. K.; Singh, M.

2018-02-01

Heat exchangers are widely used in various energy-recovery applications. However, for specific applications where metallic tubes are subjected to various drawbacks i.e. cost, weight, corrosion etc. polymer materials are promising alternatives. In present study, various conventional as well as promising alternatives materials are chosen for investigation computationally. Experimentally, bi-annulus heat exchanger configuration is investigated for metallic materials. The simulations carried out conclude that the dimensionless temperature parameter for Cross-linked polypropylethylene (PEX) is greater than other polymers. It increases with increasing axial length of tube. The value for dimensionless temperature is higher for copper which is used as conventional tube material. Among different polymers highest temperature is observed for PEX followed by Low density polypropylene (LDPE), Polypropylene (PP) and Polyvinylidene fluoride (PVDF). For axial length up to 70mm approx. the temperature rises for PEX, LDPE is 28.3% and 26.4% respectively. However, temperature variation is same for PP and PVDF for same axial distance. This temperature variation is increased to 72.4%, 67.2%, 58.62% and 56.89% for PEX, LDPE, PP and PVDF respectively as axial distance variation reaches the end of pipe. The inner annulus temperature for PEX material at 10% length of tube is 28.3% of temperature achieved in copper tube which increases to 72.4% for full length of tube.

Selective recovery of gold from waste mobile phone PCBs by hydrometallurgical process.

PubMed

Kim, Eun-young; Kim, Min-seuk; Lee, Jae-chun; Pandey, B D

2011-12-30

The leaching of gold from the scrap mobile phone PCBs by electro-generated chlorine as an oxidant and its recovery by ion exchange process was investigated. The leaching experiments were carried out by employing separate leaching reactor connected with the anode compartment of a Cl(2) gas generator. The leaching of gold increased with increase in temperature and initial concentration of chlorine, and was favorable even at low concentration of acid, whereas copper leaching increased with increase in concentration of acid and decrease in temperature. In a two-stage leaching process, copper was mostly dissolved (97%) in 165 min at 25°C during the 1st stage leaching in 2.0 mol/L HCl by electro-generated chlorine at a current density of 714A/m(2) along with a minor recovery of gold (5%). In the 2nd stage gold was mostly leached out (93% recovery, ∼67 mg/L) from the residue of the 1st stage by the electro-generated chlorine in 0.1 mol/L HCl. Gold recovery from the leach liquor by ion exchange using Amberlite XAD-7HP resin was found to be 95% with the maximum amount of gold adsorbed as 46.03 mg/g resin. A concentrated gold solution, 6034 mg/L with 99.9% purity was obtained in the ion exchange process. Copyright © 2011 Elsevier B.V. All rights reserved.

Monocopper active site for partial methane oxidation in Cu-exchanged 8MR zeolites

DOE PAGES

Kulkarni, Ambarish R.; Zhao, Zhi -Jian; Siahrostami, Samira; ...

2016-08-17

Direct conversion of methane to methanol using oxygen is experiencing renewed interest owing to the availability of new natural gas resources. Copper-exchanged zeolites such as mordenite and ZSM-5 have shown encouraging results, and di- and tri-copper species have been suggested as active sites. Recently, small eight-membered ring (8MR) zeolites including SSZ-13, -16, and -39 have been shown to be active for methane oxidation, but the active sites and reaction mechanisms in these 8MR zeolites are not known. In this work, we use density functional theory (DFT) calculations to systematically evaluate monocopper species as active sites for the partial methane oxidationmore » reaction in Cu-exchanged SSZ-13. On the basis of kinetic and thermodynamic arguments, we suggest that [Cu IIOH] + species in the 8MR are responsible for the experimentally observed activity. Furthermore, our results successfully explain the available spectroscopic data and experimental observations including (i) the necessity of water for methanol extraction and (ii) the effect of Si/Al ratio on the catalyst activity. Monocopper species have not yet been suggested as an active site for the partial methane oxidation reaction, and our results suggest that [Cu IIOH] + active site may provide complementary routes for methane activation in zeolites in addition to the known [Cu–O–Cu] 2+ and Cu 3O 3 motifs.« less

In situ modification of chromatography adsorbents using cold atmospheric pressure plasmas

NASA Astrophysics Data System (ADS)

Olszewski, P.; Willett, T. C.; Theodosiou, E.; Thomas, O. R. T.; Walsh, J. L.

2013-05-01

Efficient manufacturing of increasingly sophisticated biopharmaceuticals requires the development of new breeds of chromatographic materials featuring two or more layers, with each layer affording different functions. This letter reports the in situ modification of a commercial beaded anion exchange adsorbent using atmospheric pressure plasma generated within gas bubbles. The results show that exposure to He-O2 plasma in this way yields significant reductions in the surface binding of plasmid DNA to the adsorbent exterior, with minimal loss of core protein binding capacity; thus, a bi-layered chromatography material exhibiting both size excluding and anion exchange functionalities within the same bead is produced.

Shrink wrapping redox-active crystals of polyoxometalate open frameworks with organic polymers via crystal induced polymerisation.

PubMed

Takashima, Yohei; Miras, Haralampos N; Glatzel, Stefan; Cronin, Leroy

2016-06-14

We report examples of crystal surface modification of polyoxometalate open frameworks whereby the use of pyrrole or aniline as monomers leads to the formation of the corresponding polymers via an oxidative polymerization process initiated by the redox active POM scaffolds. Guest-exchange experiments demonstrate that the polymers can finely tune the guest exchange rate and their structural integrity is retained after the surface modifications. In addition, the formation of polyoxometalate-based self-fabricating tubes by the dissolution of Keggin-based network crystals were also modulated by the polymers, allowing a new type of hybrid inorganic polymer with an organic coating to be fabricated.

Food Exchange List and Dietary Management of Non-Communicable Diseases in Cultural Perspective.

PubMed

Khan, Mahnaz Nasir; Kalsoom, Samia; Khan, Ayyaz Ali

2017-01-01

This review focuses at highlighting the importance of Food Exchange List in cultural perspective, as an effective dietary tool to help individuals' manage their dietary modifications in relation to non communicable diseases whilst specifying measures that can help improve the quality of Food Exchange Lists for combating various non communicable diseases and addressing adherence related issues to specialized diets. A search was done using PubMed & Google Scholar till June 2016. Search terms used were food exchange list AND disease, diet AND non-communicable diseases. We included only studies that discussed Food Exchange List (FEL) in relation to non-communicable diseases; in addition to factors like cultural relevance and adherence. Out of the 837 papers accessed 57 were identified as relevant to the Food Exchange List, out of which 39 papers were focused to the concept and development of the Food Exchange List. Only 18 discussed FEL in relation to non communicable diseases and were thus included in the review. Food exchange list is a user friendly tool for dietary modification due to disease. This tool may help to customize meals for people as it provides information regarding various food items in different groups. This tool is helpful in reducing blood & plasma glucose levels, maintaining lipid profile & effectively combating other diet related diseases & those ailments in which diet plays a significant role in maintenance & prevention from reoccurrences. However, better management and adherence to modified diets for non communicable diseases can be ensured by keeping cultural relevance under consideration before using Food Exchange Lists for such diseases.

The local environment of Cu+ in Cu-Y zeolite and its relationship to the synthesis of dimethyl carbonate.

PubMed

Drake, Ian J; Zhang, Yihua; Briggs, Daniel; Lim, Bomyi; Chau, Tanguy; Bell, Alexis T

2006-06-22

Cu-exchanged Y zeolite was investigated in order to determine the location of the copper cations relative to the zeolite framework and to determine which Cu cations are active for the oxidative carbonylation of methanol to dimethyl carbonate (DMC). Cu-Y zeolite was prepared by vapor-phase exchange of H-Y with CuCl. The oxidation state, local coordination, and bond distances of Al and Cu were determined using Al K-edge and Cu K-edge X-ray absorption spectroscopy (XAS). Complimentary information was obtained by H2 temperature-programmed reduction and by in-situ infrared spectroscopy. Cu-Y has a Cu/Al ratio of unity and very little occluded CuCl. The average Al-O and Al-Cu bond distances are 1.67 angstroms and 2.79 angstroms, respectively, and the average Cu-O and Cu-Si(Al) bond distances are 1.99 angstroms and 3.13 angstroms, respectively. All of the Cu exchanged is present as Cu+ in sites I', II, and III'. Cu-Y is active for the oxidative carbonylation of methanol, and at low reactant contact time produces DMC as the primary product. With increasing reactant contact time, DMC formation decreases in preference to the formation of dimethoxy methane (DMM) and methylformate (MF). The formation of DMM and MF is attributed to the hydrogenation of DMC and the hydrogenolysis of DMM, respectively. Observation of the catalyst under reaction conditions reveals that most of the copper cations remain as Cu+, but some oxidation of Cu+ to Cu2+ does occur. It is also concluded that only those copper cations present in site II and III' positions are accessible to the reactants, and hence are catalytically active. The dominant adsorbed species on the surface are methoxy groups, and adsorbed CO is present as a minority species. The relationship of these observations to the kinetics of DMC synthesis is discussed.

Assessment and modification of an ion source grid design in KSTAR neutral beam system.

PubMed

Lee, Dong Won; Shin, Kyu In; Jin, Hyung Gon; Choi, Bo Guen; Kim, Tae-Seong; Jeong, Seung Ho

2014-02-01

A new 2 MW NB (Neutral Beam) ion source for supplying 3.5 MW NB heating for the KSTAR campaign was developed in 2012 and its grid was made from OFHC (Oxygen Free High Conductivity) copper with rectangular cooling channels. However, the plastic deformation such as a bulging in the plasma grid of the ion source was found during the overhaul period after the 2012 campaign. A thermal-hydraulic and a thermo-mechanical analysis using the conventional code, ANSYS, were carried out and the thermal fatigue life assessment was evaluated. It was found that the thermal fatigue life of the OFHC copper grid was about 335 cycles in case of 0.165 MW/m(2) heat flux and it gave too short fatigue life to be used as a KSTAR NB ion source grid. To overcome the limited fatigue life of the current design, the following methods were proposed in the present study: (1) changing the OHFC copper to CuCrZr, copper-alloy or (2) adopting a new design with a pure Mo metal grid and CuCrZr tubes. It is confirmed that the proposed methods meet the requirements by performing the same assessment.

Regulation of Intracellular Copper by Induction of Endogenous Metallothioneins Improves the Disease Course in a Mouse Model of Amyotrophic Lateral Sclerosis.

PubMed

Tokuda, Eiichi; Watanabe, Shunsuke; Okawa, Eriko; Ono, Shin-ichi

2015-04-01

Mutations in SOD1 cause amyotrophic lateral sclerosis (ALS), an incurable motor neuron disease. The pathogenesis of the disease is poorly understood, but intracellular copper dyshomeostasis has been implicated as a key process in the disease. We recently observed that metallothioneins (MTs) are an excellent target for the modification of copper dyshomeostasis in a mouse model of ALS (SOD1(G93A)). Here, we offer a therapeutic strategy designed to increase the level of endogenous MTs. The upregulation of endogenous MTs by dexamethasone, a synthetic glucocorticoid, significantly improved the disease course and rescued motor neurons in SOD1(G93A) mice, even if the induction was initiated when peak body weight had decreased by 10%. Neuroprotection was associated with the normalization of copper dyshomeostasis, as well as with decreased levels of SOD1(G93A) aggregates. Importantly, these benefits were clearly mediated in a MT-dependent manner, as dexamethasone did not provide any protection when endogenous MTs were abolished from SOD1(G93A) mice. In conclusion, the upregulation of endogenous MTs represents a promising strategy for the treatment of ALS linked to mutant SOD1.

Reactions of copper macrocycles with antioxidants and HOCl: potential for biological redox sensing.

PubMed

Sowden, Rebecca J; Trotter, Katherine D; Dunbar, Lynsey; Craig, Gemma; Erdemli, Omer; Spickett, Corinne M; Reglinski, John

2013-02-01

A series of simple copper N(2)S(2) macrocycles were examined for their potential as biological redox sensors, following previous characterization of their redox potentials and crystal structures. The divalent species were reduced by glutathione or ascorbate at a biologically relevant pH in aqueous buffer. A less efficient reduction was also achieved by vitamin E in DMSO. Oxidation of the corresponding univalent copper species by sodium hypochlorite resulted in only partial (~65 %) recovery of the divalent form. This was concluded to be due to competition between metal oxidation and ligand oxidation, which is believed to contribute to macrocycle demetallation. Electrospray mass spectrometry confirmed that ligand oxidation had occurred. Moreover, the macrocyclic complexes could be demetallated by incubation with EDTA and bovine serum albumin, demonstrating that they would be inappropriate for use in biological systems. The susceptibility to oxidation and demetallation was hypothesized to be due to oxidation of the secondary amines. Consequently these were modified to incorporate additional oxygen donor atoms. This modification led to greater resistance to demetallation and ligand oxidation, providing a better platform for further development of copper macrocycles as redox sensors for use in biological systems.

Semi-aerobic stabilized landfill leachate treatment by ion exchange resin: isotherm and kinetic study

NASA Astrophysics Data System (ADS)

Zamri, Mohd Faiz Muaz Ahmad; Kamaruddin, Mohamad Anuar; Yusoff, Mohd Suffian; Aziz, Hamidi Abdul; Foo, Keng Yuen

2017-05-01

This study was carried out to investigate the treatability of ion exchange resin (Indion MB 6 SR) for the removal of chromium (VI), aluminium (III), zinc (II), copper (II), iron (II), and phosphate (PO4)3-, chemical oxygen demand (COD), ammonia nitrogen (NH3-N) and colour from semi-aerobic stabilized leachate by batch test. A range of ion exchange resin dosage was tested towards the removal efficiency of leachate parameters. It was observed that equilibrium data were best represented by the Langmuir model for metal ions and Freundlich was ideally fit for COD, NH3-N and colour. Intra particle diffusion model, pseudo first-order and pseudo second-order isotherm models were found ideally fit with correlation of the experimental data. The findings revealed that the models could describe the ion exchange kinetic behaviour efficiently, which further suggests comprehensive outlook for the future research in this field.

Open-cycle magnetohydrodynamic power plant based upon direct-contact closed-loop high-temperature heat exchanger

DOEpatents

Berry, G.F.; Minkov, V.; Petrick, M.

1981-11-02

A magnetohydrodynamic (MHD) power generating system is described in which ionized combustion gases with slag and seed are discharged from an MHD combustor and pressurized high temperature inlet air is introduced into the combustor for supporting fuel combustion at high temperatures necessary to ionize the combustion gases, and including a heat exchanger in the form of a continuous loop with a circulating heat transfer liquid such as copper oxide. The heat exchanger has an upper horizontal channel for providing direct contact between the heat transfer liquid and the combustion gases to cool the gases and condense the slag which thereupon floats on the heat transfer liquid and can be removed from the channel, and a lower horizontal channel for providing direct contact between the heat transfer liquid and pressurized air for preheating the inlet air. The system further includes a seed separator downstream of the heat exchanger.

Open-cycle magnetohydrodynamic power plant based upon direct-contact closed-loop high-temperature heat exchanger

DOEpatents

Berry, Gregory F.; Minkov, Vladimir; Petrick, Michael

1988-01-05

A magnetohydrodynamic (MHD) power generating system in which ionized combustion gases with slag and seed are discharged from an MHD combustor and pressurized high temperature inlet air is introduced into the combustor for supporting fuel combustion at high temperatures necessary to ionize the combustion gases, and including a heat exchanger in the form of a continuous loop with a circulating heat transfer liquid such as copper oxide. The heat exchanger has an upper horizontal channel for providing direct contact between the heat transfer liquid and the combustion gases to cool the gases and condense the slag which thereupon floats on the heat transfer liquid and can be removed from the channel, and a lower horizontal channel for providing direct contact between the heat transfer liquid and pressurized air for preheating the inlet air. The system further includes a seed separator downstream of the heat exchanger.

Open-cycle magnetohydrodynamic power plant based upon direct-contact closed-loop high-temperature heat exchanger

DOEpatents

Berry, Gregory F.; Minkov, Vladimir; Petrick, Michael

1988-01-01

A magnetohydrodynamic (MHD) power generating system in which ionized combustion gases with slag and seed are discharged from an MHD combustor and pressurized high temperature inlet air is introduced into the combustor for supporting fuel combustion at high temperatures necessary to ionize the combustion gases, and including a heat exchanger in the form of a continuous loop with a circulating heat transfer liquid such as copper oxide. The heat exchanger has an upper horizontal channel for providing direct contact between the heat transfer liquid and the combustion gases to cool the gases and condense the slag which thereupon floats on the heat transfer liquid and can be removed from the channel, and a lower horizontal channel for providing direct contact between the heat transfer liquid and pressurized air for preheating the inlet air. The system further includes a seed separator downstream of the heat exchanger.

Brayton-cycle heat exchanger technology program

NASA Technical Reports Server (NTRS)

Killackey, J. J.; Coombs, M. G.; Graves, R. F.; Morse, C. J.

1976-01-01

The following five tasks designed to advance this development of heat exchanger systems for close loop Brayton cycle power systems are presented: (1) heat transfer and pressure drop data for a finned tubular heat transfer matrix. The tubes are arranged in a triangular array with copper stainless steel laminate strips helically wound on the tubes to form a disk fin geometry; (2) the development of a modularized waste heat exchanger. Means to provide verified double containment are described; (3) the design, fabrication, and test of compact plate fin heat exchangers representative of full scale Brayton cycle recuperators; (4) the analysis and design of bellows suitable for operation at 1600 F and 200 psia for 1,000 cycles and 50,000 hours creep life; and (5) screening tests used to select a low cost braze alloy with the desirable attributes of a gold base alloy. A total of 22 different alloys were investigated; the final selection was Nicrobraz 30.

Electron Spin Resonance in CuSO45H2O down to 100 mK

NASA Astrophysics Data System (ADS)

Kadowaki, Kazuo; Chiba, Yoshiaki; Kindo, Koichi; Date, Muneyuki

1988-12-01

Copper sulfate pentahydrate CuSO45H2O is investigated by ESR at 9, 17, 24, 35 and 50 GHz regions down to about 100 mK using a combined cryostat of 3He and adiabatic demagnetization. The temperature dependent exchange interaction JAB between inequivalent site spins A and B is found. It is about 0.11 K at room temperature and increases with decreasing temperature up to 0.24 K. Temperature dependent resonance shifts are attributed to the exchange shift coming from non-resonant dissimilar spins. Partial order effect below 1 K is discussed.

Effect of bentonite modification on hardness and mechanical properties of natural rubber nanocomposites

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

Santiago, Denise Ester O.; Department of Chemical Engineering, University of the Philippines, Los Baños, College, Laguna 4031 Philippines; Pajarito, Bryan B.

The effect of sodium activation, ion-exchange with tertiary amine salt, surface treatment with non-ionic surfactant, and wet grinding of bentonite on hardness and mechanical properties of natural rubber nanocomposites (NRN) was studied using full factorial design of experiment. Results of X-ray diffraction (XRD) show increase in basal spacing d of bentonite due to modification, while attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirm the organic modification of bentonite. Analysis of variance (ANOVA) shows that the main effect of surface treatment increases the hardness and decreases the tensile modulus of the NRN. The surface treatment and wet grinding of bentonitemore » decrease the tensile stresses at 100, 200 and 300% strain of NRN. Sodium activation and ion-exchange negatively affect the compressive properties, while surface treatment significantly improves the compressive properties of NRN.« less

Accumulation, distribution, and toxicity of copper in sediments of catfish ponds receiving periodic copper sulfate applications.

PubMed

Han, F X; Hargreaves, J A; Kingery, W L; Huggett, D B; Schlenk, D K

2001-01-01

Copper sulfate (CuSO4) is applied periodically to commercial channel catfish (Ictalurus panctatus) ponds as an algicide or parasiticide. Current understanding of the chemistry of copper in soil-water systems suggests that copper may accumulate in pond sediments, although the forms and potential bioavailability of copper in catfish pond sediments are not known. This study investigated the accumulation and distribution of copper in the sediment of catfish ponds receiving periodic additions of CuSO4.5H2O. All ponds were constructed in Sharkey (very-fine, smectitic, thermic Chromic Epiaquert) soil. Nine 0.40-ha ponds received 59 applications of 2.27 kg CuSO4.5H2O per application per pond over 3 yr; no CuSO4.5H2O applications were made to nine additional ponds. Total Cu concentration in the sediments of CuSO4.5H2O-amended catfish ponds (172.5 mg kg(-1)) was four to five times higher than that in the sediments of nonamended ponds (36.1 mg kg(-1)). Copper accumulated in catfish pond sediments at a rate of 41 microg kg(-1) dry sediment for each 1 kg ha(-1) of CuSO4. 5H2O applied to ponds. Copper in the sediments of amended ponds was mainly in the organic matter-bound (30.7%), carbonate-bound (31.8%), and amorphous iron oxide-bound (22.1%) fractions with a considerable fraction (3.4%; 3 to 8 mg kg(-1)) in soluble and exchangeable fractions. This indicates that Cu accumulates differentially in various fractions, with proportionally greater initial accumulation in potentially bioavailable forms. However, toxicity bioassays with amphipods (Hyallela azteca) and common cattail (Typha latifolia L.) indicated that the effect of exposure to amended or nonamended pond sediments was not different.

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

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

Poly(glycidyl methacrylate)-A soft template for the facile preparation of poly(glycidyl methacrylate) core-copper nanoparticle shell nanocomposite

NASA Astrophysics Data System (ADS)

Mohammed Safiullah, S.; Abdul Wasi, K.; Anver Basha, K.

2015-12-01

Poly(glycidyl methacrylate) core/copper nanoparticle shell nanocomposite (PGMA/Cu nanohybrid) was prepared by simple two step method (i) The synthesis of poly(glycidyl methacrylate) (PGMA) beads by free radical suspension polymerization followed by (ii) direct deposition of copper nanoparticles (CuNPs) on activated PGMA beads. The PGMA beads were used as a soft template to host the CuNPs without surface modification of it. In this method the CuNPs were formed by chemical reduction of copper salts using sodium borohydride in water medium and deposited directly on the activated PGMA. Two different concentrations of copper salts were employed to know the effect of concentration on the shape and size of nanoparticles. The results showed that, the different sizes and shapes of CuNPs were deposited on the PGMA matrix. The X-ray Diffraction study results showed that the CuNPs were embedded on the surface of the PGMA matrix. The scanning electron microscopic images revealed that the fabrication of CuNPs on the PGMA matrix possess different shapes and changes the morphology and nature of PGMA beads significantly. The fluorescent micrograph also confirmed that the CuNPs were doped on the PGMA surface. The thermal studies have demonstrated that the CuNPs deposition on the surface of PGMA beads had a significant effect.

Effects of spin-orbit coupling and many-body correlations in STM transport through copper phthalocyanine.

PubMed

Siegert, Benjamin; Donarini, Andrea; Grifoni, Milena

2015-01-01

The interplay of exchange correlations and spin-orbit interaction (SOI) on the many-body spectrum of a copper phtalocyanine (CuPc) molecule and their signatures in transport are investigated. We first derive a minimal model Hamiltonian in a basis of frontier orbitals that is able to reproduce experimentally observed singlet-triplet splittings. In a second step SOI effects are included perturbatively. Major consequences of the SOI are the splitting of former degenerate levels and a magnetic anisotropy, which can be captured by an effective low-energy spin Hamiltonian. We show that scanning tunneling microscopy-based magnetoconductance measurements can yield clear signatures of both these SOI-induced effects.

Remote C-H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling.

PubMed

Xu, Jun; Shen, Chao; Zhu, Xiaolei; Zhang, Pengfei; Ajitha, Manjaly J; Huang, Kuo-Wei; An, Zhongfu; Liu, Xiaogang

2016-03-18

Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polypyrrole Coated Cellulosic Substrate Modified by Copper Oxide as Electrode for Nitrate Electroreduction

NASA Astrophysics Data System (ADS)

Hamam, A.; Oukil, D.; Dib, A.; Hammache, H.; Makhloufi, L.; Saidani, B.

2015-08-01

The aim of this work is to synthesize polypyrrole (PPy) films on nonconducting cellulosic substrate and modified by copper oxide particles for use in the nitrate electroreduction process. Firstly, the chemical polymerization of polypyrrole onto cellulosic substrate is conducted by using FeCl3 as an oxidant and pyrrole as monomer. The thickness and topography of the different PPy films obtained were estimated using a profilometer apparatus. The electrochemical reactivity of the obtained electrodes was tested by voltamperometry technique and electrochemical impedance spectroscopy. Secondly, the modification of the PPy film surface by incorporation of copper oxide particles is conducted by applying a galvanostatic procedure from a CuCl2 solution. The SEM, EDX and XRD analysis showed the presence of CuO particles in the polymer films with dimensions less than 50 nm. From cyclic voltamperometry experiments, the composite activity for the nitrate electroreduction reaction was evaluated and the peak of nitrate reduction is found to vary linearly with initial nitrate concentration.

77 FR 45721 - Consolidated Audit Trail

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-01

...The Securities and Exchange Commission (``Commission'') is adopting Rule 613 under the Securities Exchange Act of 1934 (``Exchange Act'' or ``Act'') to require national securities exchanges and national securities associations (``self-regulatory organizations'' or ``SROs'') to submit a national market system (``NMS'') plan to create, implement, and maintain a consolidated order tracking system, or consolidated audit trail, with respect to the trading of NMS securities, that would capture customer and order event information for orders in NMS securities, across all markets, from the time of order inception through routing, cancellation, modification, or execution.

Theoretical modeling of the electronic structure and exchange interactions in Cu(II)Pc

NASA Astrophysics Data System (ADS)

Wu, Wei; Fisher, A. J.; Harrison, N. M.; Wang, Hai; Wu, Zhenlin; Gardener, Jules; Heutz, Sandrine; Jones, Tim; Aeppli, Gabriel

2012-12-01

We calculate the electronic structure and exchange interactions in a copper(II)phthalocyanine (Cu(II)Pc) crystal as a one-dimensional molecular chain using hybrid exchange density functional theory (DFT). In addition, the intermolecular exchange interactions are also calculated in a molecular dimer using Green's function perturbation theory (GFPT) to illustrate the underlying physics. We find that the exchange interactions depend strongly on the stacking angle, but weakly on the sliding angle (defined in the text). The hybrid DFT calculations also provide an insight into the electronic structure of the Cu(II)Pc molecular chain and demonstrate that on-site electron correlations have a significant effect on the nature of the ground state, the band gap and magnetic excitations. The exchange interactions predicted by our DFT calculations and GFPT calculations agree qualitatively with the recent experimental results on newly found η-Cu(II)Pc and the previous results for the α- and β-phases. This work provides a reliable theoretical basis for the further application of Cu(II)Pc to molecular spintronics and organic-based quantum information processing.

Theoretical modeling of the electronic structure and exchange interactions in a Cu(II)Pc one-dimensional chain

NASA Astrophysics Data System (ADS)

Wu, Wei; Fisher, A. J.; Harrison, N. M.

2011-07-01

We calculate the electronic structure and exchange interactions in a copper(II)phthalocyanine [Cu(II)Pc] crystal as a one-dimensional molecular chain using hybrid exchange density functional theory (DFT). In addition, the intermolecular exchange interactions are also calculated in a molecular dimer using Green’s function perturbation theory (GFPT) to illustrate the underlying physics. We find that the exchange interactions depend strongly on the stacking angle, but weakly on the sliding angle (defined in the text). The hybrid DFT calculations also provide an insight into the electronic structure of the Cu(II)Pc molecular chain and demonstrate that on-site electron correlations have a significant effect on the nature of the ground state, the band gap, and magnetic excitations. The exchange interactions predicted by our DFT calculations and GFPT calculations agree qualitatively with the recent experimental results on newly found η-Cu(II)Pc and the previous results for the α and β phases. This work provides a reliable theoretical basis for the further application of Cu(II)Pc to molecular spintronics and organic-based quantum information processing.

Binding characteristics of copper and cadmium by cyanobacterium Spirulina platensis.

PubMed

Fang, Linchuan; Zhou, Chen; Cai, Peng; Chen, Wenli; Rong, Xingmin; Dai, Ke; Liang, Wei; Gu, Ji-Dong; Huang, Qiaoyun

2011-06-15

Cyanobacteria are promising biosorbent for heavy metals in bioremediation. Although sequestration of metals by cyanobacteria is known, the actual mechanisms and ligands involved are not very well understood. The binding characteristics of Cu(II) and Cd(II) by the cyanobacterium Spirulina platensis were investigated using a combination of chemical modifications, batch adsorption experiments, Fourier transform infrared (FTIR) spectroscopy and X-ray absorption fine structure (XAFS) spectroscopy. A significant increase in Cu(II) and Cd(II) binding was observed in the range of pH 3.5-5.0. Dramatical decrease in adsorption of Cu(II) and Cd(II) was observed after methanol esterification of the nonliving cells demonstrating that carboxyl functional groups play an important role in the binding of metals by S. platensis. The desorption rate of Cu(II) and Cd(II) from S. platensis surface was 72.7-80.7% and 53.7-58.0% by EDTA and NH(4)NO(3), respectively, indicating that ion exchange and complexation are the dominating mechanisms for Cu(II) and Cd(II) adsorption. XAFS analysis provided further evidence on the inner-sphere complexation of Cu by carboxyl ligands and showed that Cu is complexed by two 5-membered chelate rings on S. platensis surface. Copyright © 2011 Elsevier B.V. All rights reserved.

The development of a fiber optics communication network for controlling a Multidegree-Of-Freedom Serpentine Truss

NASA Astrophysics Data System (ADS)

Andrawis, Alfred S.

1994-10-01

The problem addressed by this report is the large size and heavy weight of the cable bundle, used for controlling a Multidegree-Of-Freedom Serpentine Truss Manipulator arm, which imposes limitations on the manipulator arm maneuverability. This report covers a design of an optical fiber network to replace the existing copper wire network of the Serpentine Truss Manipulator. This report proposes a fiber network design which significantly reduces the bundle size into two phases. The first phase does not require any modifications for the manipulator architecture, while the other requires major modifications. Design philosophy, hardware details and schematic diagrams are presented.

The development of a fiber optics communication network for controlling a Multidegree-Of-Freedom Serpentine Truss

NASA Technical Reports Server (NTRS)

Andrawis, Alfred S.

1994-01-01

The problem addressed by this report is the large size and heavy weight of the cable bundle, used for controlling a Multidegree-Of-Freedom Serpentine Truss Manipulator arm, which imposes limitations on the manipulator arm maneuverability. This report covers a design of an optical fiber network to replace the existing copper wire network of the Serpentine Truss Manipulator. This report proposes a fiber network design which significantly reduces the bundle size into two phases. The first phase does not require any modifications for the manipulator architecture, while the other requires major modifications. Design philosophy, hardware details and schematic diagrams are presented.

Effect of pentacene/Ag anode buffer and UV-ozone treatment on durability of small-molecule organic solar cells

NASA Astrophysics Data System (ADS)

Inagaki, S.; Sueoka, S.; Harafuji, K.

2017-06-01

Three surface modifications of indium tin oxide (ITO) are experimentally investigated to improve the performance of small-molecule organic solar cells (OSCs) with an ITO/anode buffer layer (ABL)/copper phthalocyanine (CuPc)/fullerene/bathocuproine/Ag structure. An ultrathin Ag ABL and ultraviolet (UV)-ozone treatment of ITO independently improve the durability of OSCs against illumination stress. The thin pentacene ABL provides good ohmic contact between the ITO and the CuPc layer, thereby producing a large short-circuit current. The combined use of the abovementioned three modifications collectively achieves both better initial performance and durability against illumination stress.

77 FR 68193 - Self-Regulatory Organizations; NYSE Arca, Inc.; Order Granting Approval of Proposed Rule Change...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-15

... Available Under the Short Term Option Series Program (``STOS Program''), To Allow for the Exchange To Delist... Program Under Limited Circumstances November 8, 2012. I. Introduction On September 6, 2012, NYSE Arca, Inc...'') to make certain modifications to the Exchange's Short Term Option Series Program (``STOS Program...

75 FR 21061 - Self-Regulatory Organizations; Chicago Stock Exchange, Inc.; Notice of Filing of Proposed Rule...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-22

... exchange to a fully automated limit-order matching system. This filing would alter or eliminate references... Article 6, Rule 11 (Continuing Education for Registered Persons), we are deleting the rule text which was..., which addressed cancellation or modification of transactions due to systems malfunctions or disruptions...

Surface monofunctionalized polymethyl pentene hollow fiber membranes by plasma treatment and hemocompatibility modification for membrane oxygenators

NASA Astrophysics Data System (ADS)

Huang, Xin; Wang, Weiping; Zheng, Zhi; Fan, Wenling; Mao, Chun; Shi, Jialiang; Li, Lei

2016-01-01

The hemocompatibility of polymethyl pentene (PMP) hollow fiber membranes (HFMs) was improved through surface modification for membrane oxygenator applications. The modification was performed stepwise with the following: (1) oxygen plasma treatment, (2) functionalization of monosort hydroxyl groups through NaBH4 reduction, and (3) grafting 2-methacryloyloxyethyl phosphorylcholine (MPC) or heparin. SEM, ATR-FTIR, and XPS analyses were conducted to confirm successful grafting during the modification. The hemocompatibility of PMP HFMs was analyzed and compared through protein adsorption, platelet adhesion, and coagulation tests. Pure CO2 and O2 permeation rates, as well as in vitro gas exchange rates, were determined to evaluate the mass transfer properties of PMP HFMs. SEM results showed that different nanofibril topographies were introduced on the HFM surface. ATR-FTIR and XPS spectra indicated the presence of functionalization of monosort hydroxyl group and the grafting of MPC and heparin. Hemocompatibility evaluation results showed that the modified PMP HFMs presented optimal hemocompatibility compared with pristine HFMs. Gas permeation results revealed that gas permeation flux increased in the modified HFMs because of dense surface etching during the plasma treatment. The results of in vitro gas exchange rates showed that all modified PMP HFMs presented decreased gas exchange rates because of potential surface fluid wetting. The proposed strategy exhibits a potential for fabricating membrane oxygenators for biomedical applications to prevent coagulation formation and alter plasma-induced surface topology and composition.

AN ENVIRONMENTAL AND ECONOMIC COMPARISON OF ION EXCHANGE AND RECENTLY COMMERCIALIZED ELECTROCHEMICAL TECHNOLOGIES FOR THE RECOVERY OF RINSE WATER IN BRIGHT NICKEL PLATING FACILITY

EPA Science Inventory

Researchers at USEPA are testing and evaluating two commercial electrochemical technologies for the purification of rinse water and the recovery of copper and nickel from a variety of electroplating processes. One of the investigated technologies is based on the application of hi...

77 FR 11602 - Self-Regulatory Organizations; The NASDAQ Stock Market LLC; Notice of Filing and Immediate...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-27

... offers various bandwidth options for connectivity to NASDAQ, including a 10Gb fiber connection, a 1Gb copper connection, and a 100 MB connection.\\3\\ In keeping with changes in technology, the Exchange now proposes to provide an enhanced bandwidth option to enable its clients a more efficient connection to the...

Preventing Clogging In A Vacuum Plasma Spray Gun

NASA Technical Reports Server (NTRS)

Krotz, Phillip D.; Daniel, Ronald L., Jr.; Davis, William M.

1994-01-01

Modification of powder-injection ports enables lengthy, high-temperature deposition operations. Graphite inserts prevent clogging of ports through which copper powder injected into vacuum plasma spray (VPS) gun. Graphite liners eliminate need to spend production time refurbishing VPS gun, reducing cost of production and increasing productivity. Concept also applied to other material systems used for net-shape fabrication via VPS.

75 FR 16179 - Notice of Affirmative Decisions on Petitions for Modification Granted in Whole or in Part

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-31

...-013-C FR Notice: 74 FR 27185 (June 8, 2009). Petitioner: Wolf Run Mining Company, Rt. 3, Box 146... FR 23745 (May 20, 2009). Petitioner: Excel Mining, LLC, Box 4126, State Highway 194 West, Pikeville... Heights, P.O. Box 1944, Superior, Arizona 85273. Mine: Resolution Copper Mine, MSHA I.D. No. 02-00152...

Tailoring gas-phase CO2 electroreduction selectivity to hydrocarbons at Cu nanoparticles

NASA Astrophysics Data System (ADS)

Merino-Garcia, I.; Albo, J.; Irabien, A.

2018-01-01

Copper-based surfaces appear as the most active catalysts for CO2 electroreduction to hydrocarbons, even though formation rates and efficiencies still need to be improved. The aim of the present work is to evaluate the continuous gas-phase CO2 electroreduction to hydrocarbons (i.e. ethylene and methane) at copper nanoparticulated-based surfaces, paying attention to particle size influence (ranging from 25-80 nm) on reaction productivity, selectivity, and Faraday efficiency (FE) for CO2 conversion. The effect of the current density and the presence of a microporous layer within the working electrode are then evaluated. Copper-based gas diffusion electrodes are prepared by airbrushing the catalytic ink onto carbon supports, which are then coupled to a cation exchange membrane (Nafion) in a membrane electrode assembly. The results show that the use of smaller copper nanoparticles (25 nm) leads to a higher ethylene production (1148 μmol m-2 s-1) with a remarkable high FE (92.8%), at the same time, diminishing the competitive hydrogen evolution reaction in terms of FE. This work demonstrates the importance of nanoparticle size on reaction selectivity, which may be of help to design enhanced electrocatalytic materials for CO2 valorization to hydrocarbons.

The beginning of metallurgy in the southern Levant: a late 6th millennium CalBC copper awl from Tel Tsaf, Israel.

PubMed

Garfinkel, Yosef; Klimscha, Florian; Shalev, Sariel; Rosenberg, Danny

2014-01-01

The beginning of metallurgy in the ancient Near East attracts much attention. The southern Levant, with the rich assemblage of copper artifacts from the Nahal Mishmar cave and the unique gold rings of the Nahal Qanah cave, is regarded as a main center of early metallurgy during the second half of the 5th millennium CalBC. However, a recently discovered copper awl from a Middle Chalcolithic burial at Tel Tsaf, Jordan Valley, Israel, suggests that cast metal technology was introduced to the region as early as the late 6th millennium CalBC. This paper examines the chemical composition of this item and reviews its context. The results indicate that it was exported from a distant source, probably in the Caucasus, and that the location where it was found is indicative of the social status of the buried individual. This rare finding indicates that metallurgy was first diffused [corrected] to the southern Levant through exchange networks and only centuries later involved local productionThis copper awl, the earliest metal artifact found in the southern Levant, indicates that the elaborate Late Chalcolithic metallurgy developed from a more ancient tradition.

The Beginning of Metallurgy in the Southern Levant: A Late 6th Millennium CalBC Copper Awl from Tel Tsaf, Israel

PubMed Central

Garfinkel, Yosef; Klimscha, Florian; Shalev, Sariel; Rosenberg, Danny

2014-01-01

The beginning of metallurgy in the ancient Near East attracts much attention. The southern Levant, with the rich assemblage of copper artifacts from the Nahal Mishmar cave and the unique gold rings of the Nahal Qanah cave, is regarded as a main center of early metallurgy during the second half of the 5th millennium CalBC. However, a recently discovered copper awl from a Middle Chalcolithic burial at Tel Tsaf, Jordan Valley, Israel, suggests that cast metal technology was introduced to the region as early as the late 6th millennium CalBC. This paper examines the chemical composition of this item and reviews its context. The results indicate that it was exported from a distant source, probably in the Caucasus, and that the location where it was found is indicative of the social status of the buried individual. This rare finding indicates that metallurgy was first defused to the southern Levant through exchange networks and only centuries later involved local production. This copper awl, the earliest metal artifact found in the southern Levant, indicates that the elaborate Late Chalcolithic metallurgy developed from a more ancient tradition. PMID:24671185

Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes

PubMed Central

Chenette, Heather C.S.; Robinson, Julie R.; Hobley, Eboni; Husson, Scott M.

2012-01-01

This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

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

PubMed

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

2016-07-01

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

Fabrication of durable copper plating superhydrophobic surface with improved corrosion resistance and oil-water separation properties

NASA Astrophysics Data System (ADS)

Zhao, Yichao; Xiao, Xinyan; Ye, Zhihao; Ji, Qiang; Xie, Wei

2018-02-01

A mechanical durable superhydrophobic copper-plated stainless steel mesh was successfully fabricated by an electrodeposition process and 1-octadecanethiol modification. The as-prepared superhydrophobic mesh displays water contact angle of 153° and shows excellent anti-corrosion and water-oil separation properties in the condition of 0.1 A/cm2 current density for 35 s. In comparison with bare stainless steel mesh, the corrosion current of the as-prepared superhydrophobic mesh is close to 1/6 of the former. Meanwhile, the as-prepared superhydrophobic mesh could continuously separate oil from oil-water mixtures. The separation efficiency of continuous separation is as high as 96% and shows less than 1% decrease after ten cycles.

Laser direct writing of thin-film copper structures as a modification of lithographic processes

NASA Astrophysics Data System (ADS)

Meyer, F.; Ostendorf, A.; Stute, U.

2007-04-01

This paper presents a flexible, mask-free and efficient technique for UV-laser micropatterning of photosensitive resist by laser direct writing (LDW). Photo resist spun on gold sputtered silicon wafers has been laser structured by a scanner guided 266nm DPSSL and electroplated. Ablation behaviour and optimum seed layer preparation in relation to parameters like pulse energy, scanning speed and number of scanned cycles and the electroplating results are discussed. The resulting adhesive strength was measured by a µ-sear device and the gold seed layer-plated copper interface investigated by SEM and EDX to explain correlation to identified bonding behaviour. Improved adhesive strength was observed with higher laser pulse energy and reduced number of cycle.

Marker Exchange Mutagenesis of mxaF, Encoding the Large Subunit of the Mxa Methanol Dehydrogenase, in Methylosinus trichosporium OB3b

PubMed Central

Farhan Ul Haque, Muhammad; Gu, Wenyu; DiSpirito, Alan A.

2015-01-01

Methanotrophs have remarkable redundancy in multiple steps of the central pathway of methane oxidation to carbon dioxide. For example, it has been known for over 30 years that two forms of methane monooxygenase, responsible for oxidizing methane to methanol, exist in methanotrophs, i.e., soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO), and that expression of these two forms is controlled by the availability of copper. Specifically, sMMO expression occurs in the absence of copper, while pMMO expression increases with increasing copper concentrations. More recently, it was discovered that multiple forms of methanol dehydrogenase (MeDH), Mxa MeDH and Xox MeDH, also exist in methanotrophs and that the expression of these alternative forms is regulated by the availability of cerium. That is, expression of Xox MeDH increases in the presence of cerium, while Mxa MeDH expression decreases in the presence of cerium. As it had been earlier concluded that pMMO and Mxa MeDH form a supercomplex in which electrons from Mxa MeDH are back donated to pMMO to drive the initial oxidation of methane, we speculated that Mxa MeDH could be rendered inactive through marker-exchange mutagenesis but growth on methane could still be possible if cerium was added to increase the expression of Xox MeDH under sMMO-expressing conditions. Here we report that mxaF, encoding the large subunit of Mxa MeDH, could indeed be knocked out in Methylosinus trichosporium OB3b, yet growth on methane was still possible, so long as cerium was added. Interestingly, growth of this mutant occurred in both the presence and the absence of copper, suggesting that Xox MeDH can replace Mxa MeDH regardless of the form of MMO expressed. PMID:26712545

Copper-Doped Bioactive Glass as Filler for PMMA-Based Bone Cements: Morphological, Mechanical, Reactivity, and Preliminary Antibacterial Characterization.

PubMed

Miola, Marta; Cochis, Andrea; Kumar, Ajay; Arciola, Carla Renata; Rimondini, Lia; Verné, Enrica

2018-06-06

To promote osteointegration and simultaneously limit bacterial contamination without using antibiotics, we designed innovative composite cements containing copper (Cu)-doped bioactive glass powders. Cu-doped glass powders were produced by a melt and quenching process, followed by an ion-exchange process in a Cu salt aqueous solution. Cu-doped glass was incorporated into commercial polymethyl methacrylate (PMMA)-based cements with different viscosities. The realized composites were characterized in terms of morphology, composition, leaching ability, bioactivity, mechanical, and antibacterial properties. Glass powders appeared well distributed and exposed on the PMMA surface. Composite cements showed good bioactivity, evidencing hydroxyapatite precipitation on the sample surfaces after seven days of immersion in simulated body fluid. The leaching test demonstrated that composite cements released a significant amount of copper, with a noticeable antibacterial effect toward Staphylococcus epidermidis strain. Thus, the proposed materials represent an innovative and multifunctional tool for orthopedic prostheses fixation, temporary prostheses, and spinal surgery.

Separation and Recovery of Cobalt from Copper Leach Solutions

NASA Astrophysics Data System (ADS)

Jeffers, T. H.

1985-01-01

Significant amounts of cobalt, a strategic and critical metal, are present in readily accessible copper recycling leach solutions. However, cost-effective technology is not available to separate and recover the cobalt from this low-grade domestic source. The Bureau of Mines has developed a procedure using a chelating ion-exchange resin from Dow Chemical Co. to successfully extract cobalt from a pH 3.0 copper recycling solution containing only 30 mg/1 cobalt. Cyclic tests with the commercial resin XFS-4195 in 4-ft-high by 1-in.-diameter columns gave an average cobalt extraction of 95% when 65 bed volumes of solution were processed at a flow rate of 4 gpm/ft.2 Elution of the cobalt using a 50 g/l H2SO4 solution yielded an eluate containing 0.5 gli Co. Selective elution of the loaded resin and solvent extraction procedures using di-2-ethylhexyl phosphoric acid (D2EHPA) and Cyanex 272 removed the impurities and produced a cobalt sulfate solution containing 25 g/l Co.

Nonlinear isotherm and kinetics of adsorption of copper from aqueous solutions on bentonite

NASA Astrophysics Data System (ADS)

Sadeghalvad, Bahareh; Khosravi, Sara; Azadmehr, Amir Reza

2016-11-01

Bentonite is one of the most significant of clay minerals that has been studied extensively due to its potential applications in removal of various environmental pollutants. This ability is related to its high ionic exchange capacity and high specific surface area. Copper is one of the important elements of non-ferrous metals found in industrial waste waters. In the present work, the removal of copper from aqueous solutions with Iranian bentonite (from Birjand area, southeastern Iran) used without any chemical pretreatment, was studied. The experimental results were fitted by adsorption isotherms equations with two or three parameters, which include Langmuir, Freundlich, Dubinin-Radushkevich (D-R), Redlich-Peterson, Khan, and Toth models. The best correlation coefficient ( r 2) is 0.9879 observed for Langmuir model, maximum adsorption capacity of bentonite was 55.71 mg/g. The first-order and pseudo-second-order kinetic equations were used to describe the kinetics of adsorption. The experimental data were well fitted by the pseudo-second-order kinetics.

MHD Generating system

DOEpatents

Petrick, Michael; Pierson, Edward S.; Schreiner, Felix

1980-01-01

According to the present invention, coal combustion gas is the primary working fluid and copper or a copper alloy is the electrodynamic fluid in the MHD generator, thereby eliminating the heat exchangers between the combustor and the liquid-metal MHD working fluids, allowing the use of a conventional coalfired steam bottoming plant, and making the plant simpler, more efficient and cheaper. In operation, the gas and liquid are combined in a mixer and the resulting two-phase mixture enters the MHD generator. The MHD generator acts as a turbine and electric generator in one unit wherein the gas expands, drives the liquid across the magnetic field and thus generates electrical power. The gas and liquid are separated, and the available energy in the gas is recovered before the gas is exhausted to the atmosphere. Where the combustion gas contains sulfur, oxygen is bubbled through a side loop to remove sulfur therefrom as a concentrated stream of sulfur dioxide. The combustor is operated substoichiometrically to control the oxide level in the copper.

Spatial variability of total dissolved copper and copper speciation in the inshore waters of Bermuda.

PubMed

Oldham, V E; Swenson, M M; Buck, K N

2014-02-15

Total dissolved copper (Cu) and Cu speciation were examined from inshore waters of Bermuda, in October 2009 and July-August 2010, to determine the relationship between total dissolved Cu, Cu-binding ligands and bioavailable, free, hydrated Cu(2+) concentrations. Speciation was performed using competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV). Mean total dissolved Cu concentrations ranged from 1.4 nM to 19.2 nM, with lowest concentrations at sites further from shore, consistent with previous measurements in the Sargasso Sea, and localized Cu enrichment inshore in enclosed harbors. Ligand concentrations exceeded dissolved [Cu] at most sites, and [Cu(2+)] were correspondingly low at those sites, typically <10(-13) M. One site, Hamilton Harbour, was found to have [Cu] in excess of ligands, resulting in [Cu(2+)] of 10(-10.7) M, and indicating that Cu may be toxic to phytoplankton here. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biochar and compost as amendments in copper-enriched vineyard soils - stabilization or mobilization of copper?

NASA Astrophysics Data System (ADS)

Soja, Gerhard; Fristak, Vladimir; Wimmer, Bernhard; Bell, Stephen; Chamier Glisczinski, Julia; Pardeller, Georg; Dersch, Georg; Rosner, Franz; Wenzel, Walter; Zehetner, Franz

2016-04-01

Copper is an important ingredient for several fungicides that have been used in agriculture. For organic viticulture, several diseases as e.g. downy mildew (Plasmopara viticola) can only be antagonized with Cu-containing fungicides. This long-lasting dependence on Cu-fungicides has led to a gradual Cu enrichment of vineyard soils in traditional wine-growing areas, occasionally exceeding 300 mg/kg. Although these concentrations do not affect the vines or wine quality, they may impair soil microbiological functions in the top soil layer or the root growth of green cover plants. Therefore measures are demanded that reduce the bioavailability of copper, thereby reducing the ecotoxicological effects. The use of biochar and compost as soil amendment has been suggested as a strategy to immobilize Cu and reduce the exchangeable fractions. This study consisted of lab and greenhouse experiments that were designed to test the sorption and desorption behavior of copper in vineyard soils with or without biochar and/or compost as soil amendment. Slightly acidic soils (pH<6) showed a clearer biochar-induced immobilization of copper with biochar than neutral or alkaline soils. The analyses of leachate waters of microlysimeter experiments showed that the biochar effects were more evident for a reduction of the ionic form Cu2+ than for total soluble copper, even in alkaline soils. Biochar modified with citric or tartaric acid did not significantly decrease the solubility of copper based on total dissolved concentrations although CEC was higher than in unmodified biochar. Treatments consisting of compost only or that had an equal amount of compost and biochar rather had a mobilizing effect on biochar. Sorption experiments with different DOC concentrations and biochar, however, showed a positive effect on copper sorption. Apparently in vineyard soils the predisposition to form organic-Cu-complexes may outbalance the binding possibilities of these complexes to biochar, occasionally resulting in enhanced mobilization. Presumably immobilization of copper with biochar would work best in acidic soils low in organic carbon and with low or no compost addition although this might be at odds with standard vineyard soil management practices.

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The influence of clay surface modification with berberine on the sorption of anthocyanins

NASA Astrophysics Data System (ADS)

Chulkov, A. N.; Deineka, V. I.; Tikhova, A. A.; Vesentzev, A. I.; Deineka, L. A.

2012-03-01

The influence of preliminary sorption of berberine on the sorption of anthocyanins by bentonite clay was studied. The cation exchange sorption mechanism was found to be replaced by hydrophobic sorption of these compounds after clay modification with berberine. The enthalpy of sorption along the initial isotherm part changed from endothermic to exothermic.

Palmitoylation of superoxide dismutase 1 (SOD1) is increased for familial amyotrophic lateral sclerosis-linked SOD1 mutants.

PubMed

Antinone, Sarah E; Ghadge, Ghanashyam D; Lam, Tukiet T; Wang, Lijun; Roos, Raymond P; Green, William N

2013-07-26

Mutations in Cu,Zn-superoxide dismutase (mtSOD1) cause familial amyotrophic lateral sclerosis (FALS), a neurodegenerative disease resulting from motor neuron degeneration. Here, we demonstrate that wild type SOD1 (wtSOD1) undergoes palmitoylation, a reversible post-translational modification that can regulate protein structure, function, and localization. SOD1 palmitoylation was confirmed by multiple techniques, including acyl-biotin exchange, click chemistry, cysteine mutagenesis, and mass spectrometry. Mass spectrometry and cysteine mutagenesis demonstrated that cysteine residue 6 was the primary site of palmitoylation. The palmitoylation of FALS-linked mtSOD1s (A4V and G93A) was significantly increased relative to that of wtSOD1 expressed in HEK cells and a motor neuron cell line. The palmitoylation of FALS-linked mtSOD1s (G93A and G85R) was also increased relative to that of wtSOD1 when assayed from transgenic mouse spinal cords. We found that the level of SOD1 palmitoylation correlated with the level of membrane-associated SOD1, suggesting a role for palmitoylation in targeting SOD1 to membranes. We further observed that palmitoylation occurred predominantly on disulfide-reduced as opposed to disulfide-bonded SOD1, suggesting that immature SOD1 is the primarily palmitoylated species. Increases in SOD1 disulfide bonding and maturation with increased copper chaperone for SOD1 expression caused a decrease in wtSOD1 palmitoylation. Copper chaperone for SOD1 overexpression decreased A4V palmitoylation less than wtSOD1 and had little effect on G93A mtSOD1 palmitoylation. These findings suggest that SOD1 palmitoylation occurs prior to disulfide bonding during SOD1 maturation and that palmitoylation is increased when disulfide bonding is delayed or decreased as observed for several mtSOD1s.

Performance analyses of helical coil heat exchangers. The effect of external coil surface modification on heat exchanger effectiveness

NASA Astrophysics Data System (ADS)

Andrzejczyk, Rafał; Muszyński, Tomasz

2016-12-01

The shell and coil heat exchangers are commonly used in heating, ventilation, nuclear industry, process plant, heat recovery and air conditioning systems. This type of recuperators benefits from simple construction, the low value of pressure drops and high heat transfer. In helical coil, centrifugal force is acting on the moving fluid due to the curvature of the tube results in the development. It has been long recognized that the heat transfer in the helical tube is much better than in the straight ones because of the occurrence of secondary flow in planes normal to the main flow inside the helical structure. Helical tubes show good performance in heat transfer enhancement, while the uniform curvature of spiral structure is inconvenient in pipe installation in heat exchangers. Authors have presented their own construction of shell and tube heat exchanger with intensified heat transfer. The purpose of this article is to assess the influence of the surface modification over the performance coefficient and effectiveness. The experiments have been performed for the steady-state heat transfer. Experimental data points were gathered for both laminar and turbulent flow, both for co current- and countercurrent flow arrangement. To find optimal heat transfer intensification on the shell-side authors applied the number of transfer units analysis.

Correlation between pairing initiation sites, recombination nodules and meiotic recombination in Sordaria macrospora.

PubMed

Zickler, D; Moreau, P J; Huynh, A D; Slezec, A M

1992-09-01

The decrease of meiotic exchanges (crossing over and conversion) in two mutants of Sordaria macrospora correlated strongly with a reduction of chiasmata and of both types of "recombination nodules." Serial section reconstruction electron microscopy was used to compare the synapsis pattern of meiotic prophase I in wild type and mutants. First, synapsis occurred but the number of synaptonemal complex initiation sites was reduced in both mutants. Second, this reduction was accompanied by, or resulted in, modifications of the pattern of synapsis. Genetic and synaptonemal complex maps were compared in three regions along one chromosome arm divided into well marked intervals. Reciprocal exchange frequencies and number of recombination nodules correlated in wild type in the three analyzed intervals, but disparity was found between the location of recombination nodules and exchanges in the mutants. Despite the twofold exchange decrease, sections of the genome such as the short arm of chromosome 2 and telomere regions were sheltered from nodule decrease and from pairing modifications. This indicated a certain amount of diversity in the control of these features and suggested that exchange frequency was dependent not only on the amount of effective pairing but also on the localization of the pairing sites, as revealed by the synaptonemal complex progression in the mutants.

Correlation between Pairing Initiation Sites, Recombination Nodules and Meiotic Recombination in Sordaria Macrospora

PubMed Central

Zickler, D.; Moreau, PJF.; Huynh, A. D.; Slezec, A. M.

1992-01-01

The decrease of meiotic exchanges (crossing over and conversion) in two mutants of Sordaria macrospora correlated strongly with a reduction of chiasmata and of both types of ``recombination nodules.'' Serial section reconstruction electron microscopy was used to compare the synapsis pattern of meiotic prophase I in wild type and mutants. First, synapsis occurred but the number of synaptonemal complex initiation sites was reduced in both mutants. Second, this reduction was accompanied by, or resulted in, modifications of the pattern of synapsis. Genetic and synaptonemal complex maps were compared in three regions along one chromosome arm divided into well marked intervals. Reciprocal exchange frequencies and number of recombination nodules correlated in wild type in the three analyzed intervals, but disparity was found between the location of recombination nodules and exchanges in the mutants. Despite the twofold exchange decrease, sections of the genome such as the short arm of chromosome 2 and telomere regions were sheltered from nodule decrease and from pairing modifications. This indicated a certain amount of diversity in the control of these features and suggested that exchange frequency was dependent not only on the amount of effective pairing but also on the localization of the pairing sites, as revealed by the synaptonemal complex progression in the mutants. PMID:1398050

Integrated solar collector

DOEpatents

Tchernev, Dimiter I.

1985-01-01

A solar collector having a copper panel in a contiguous space relationship with a condenser-evaporator heat exchanger located under the panel, the panel having a honeycomb-like structure on its interior defining individual cells which are filled with zeolite loaded, in its adsorbed condition, with 18 to 20% by weight of water. The interior of the panel and heat exchanger are maintained at subatmospheric pressure of about 0.1 to 1 psia. The panel and heat exchanger are insulated on their lateral sides and bottoms and on the top of the heat exchange. The panel has a black coating on its top which is exposed to and absorbs solar energy. Surrounding the insulation (which supports the panel) is an extruded aluminum framework which supports a pair of spaced-apart glass panels above the solar panel. Water in conduits from a system for heating or cooling or both is connected to flow into an inlet and discharge from outlet of a finned coil received within the heat exchanger. The collector panel provides heat during the day through desorption and condensing of water vapor from the heated solar panel in the heat exchanger and cools at night by the re-adsorption of the water vapor from the heat exchanger which lowers the absolute pressure within the system and cools the heat exchange coils by evaporation.

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Federal Register 2010, 2011, 2012, 2013, 2014

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Microbial biofilms for the removal of Cu²⁺ from CMP wastewater.

PubMed

Mosier, Aaron P; Behnke, Jason; Jin, Eileen T; Cady, Nathaniel C

2015-09-01

The modern semiconductor industry relies heavily on a process known as chemical mechanical planarization, which uses physical and chemical processes to remove excess material from the surface of silicon wafers during microchip fabrication. This process results in large volumes of wastewater containing dissolved metals including copper (Cu(2+)), which must then be filtered and treated before release into municipal waste systems. We have investigated the potential use of bacterial and fungal biomass as an alternative to the currently used ion-exchange resins for the adsorption of dissolved Cu(2+) from high-throughput industrial waste streams. A library of candidate microorganisms, including Lactobacillus casei and Pichia pastoris, was screened for ability to bind Cu(2+) from solution and to form static biofilm communities within packed-bed adsorption columns. The binding efficiency of these biomass-based adsorption columns was assessed under various flow conditions and compared to that of industrially used ion-exchange resins. We demonstrated the potential to regenerate the biomass within the adsorption columns through the use of a hydrochloric acid wash, and subsequently reuse the columns for additional copper binding. While the binding efficiency and capacity of the developed L. casei/P. pastoris biomass filters was inferior to ion-exchange resin, the potential for repeated reuse of these filters, coupled with the advantages of a more sustainable "green" adsorption process, make this technique an attractive candidate for use in industrial-scale CMP wastewater treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermal oxidative degradation of ethylene tetrafluoroethylene copolymer systems

NASA Astrophysics Data System (ADS)

Elders, Jonathan Patrick

Thermo-oxidative degradation of ethylene tetrafluoroethylene (ETFE) was investigated to determine how modifications for use in an electrical wire system affected its thermal stability. Modifications included electron irradiation and subsequent cross-linking during manufacture and contact with a metal surface. Samples with irradiation histories between 0 and 48 MRads were investigated. Degradation of ETFE was enhanced by contact with a metal "conductor" surface: silver - coated copper. Polymer degradation was analyzed by weight loss kinetics (thermogravimetric analysis (TGA)), changes in polymer morphology (differential scanning calorimetry (DSC)), optical microscopy, attenuated total reflectance (ATR) infrared spectroscopy, and gas chromatography - mass spectroscopy (GC/MS). Conductor aging (copper permeation through silver with subsequent oxidation) was investigated using scanning Auger Electron Spectroscopy (AES). Conductor aging is enhanced in the presence of the polymer surface. Interactions between conductor and polymer were analyzed by optical microscopy, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The rate of polymer degradation from 220°C to 280°C was independent of time and extent of degradation, and rate was proportional to irradiation dose. The activation energy for degradation of unirradiated ETFE was 227 kJ/mol and decreased from 150 to 138 kJ/mol for ETFE irradiated to doses between 6 and 48 MRads. Rates of degradation at 300°C to 320°C were dependent on the extent of degradation. Rates of degradation at temperatures between 230°C and 310°C were an order of magnitude larger in the presence of a conductor than in its absence, and activation energies for degradation in the presence of conductor were reduced to 120 kJ/mol. Degradation was modeled as the combination of bulk polymer degradation and catalytic degradation at the polymer-metal interface. ETFE aged at 250°C in the presence or absence of a conductor exhibited a double melting endotherm. ATR spectra of aged ETFE indicated polymer oxidation. Based on AES experiments, copper permeation during aging in the presence or absence of ETFE was consistent with Fickian diffusion. The coefficient for copper diffusion through silver was approximately 10 -15 cm2/second, and catalytic ETFE degradation was proportional to conductor aging. The copper oxidized on the surface to yield a material with a stoichiometric composition of Cu3O 2.

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

Ermanoski, Ivan; Orozco, Adrian

In this report we present the development of a packed particle bed recirculator and heat exchanger. The device is intended to create countercurrent flows of packed particle beds and exchange heat between the flows. The project focused on the design, fabrication, demonstration, and modifications of a simple prototype, in order to attain high levels of heat exchange between particle flows while maintaining an effective particle conveying rate in a scalable package. Despite heat losses in a package not optimized for heat retention, 50% heat recovery was achieved, at a particle conveying efficiency of 40%.

Evidence of ammonium ion-exchange properties of natural bentonite and application to ammonium detection.

PubMed

Zazoua, A; Kazane, I; Khedimallah, N; Dernane, C; Errachid, A; Jaffrezic-Renault, N

2013-12-01

Ammonium exchange with hybrid PVC-bentonite (mineral montmorillonite clay) thin film was revealed using FTIR spectroscopy, EDX, cyclic voltammetry and electrochemical impedance spectroscopy. The effect of ammonium exchange on the charge transfer resistance of PVC-bentonite hybrid thin film was attributed to a modification of the intersheet distance and hydration of bentonite crystals. The obtained impedimetric ammonium sensor shows a linear range of detection from 10(-4)M to 1M and a detection limit around 10(-6)M. © 2013.

Cryogenic cooler apparatus

DOEpatents

Wheatley, J.C.; Paulson, D.N.; Allen, P.C.

1983-01-04

A Malone-type final stage for utilization in a Stirling cycle cryogenic cooler apparatus includes a displacer slidable within a vessel. [sup 4]He, [sup 3]He, or a mixture thereof is made to flow in a pulsating unidirectional manner through a regenerator in the displacer by utilization of check valves in separate fluid channels. Stacked copper screen members extend through the channels and through a second static thermodynamic medium within the displacer to provide efficient lateral heat exchange and enable cooling to temperatures in the range of 3--4 K. Another embodiment utilizes sintered copper particles in the regenerator. Also described is a final stage that has a non-thermally conducting displacer having passages with check valves for directing fluid past a regenerator formed in the surrounding vessel. 10 figs.

Cryogenic cooler apparatus

DOEpatents

Wheatley, John C.; Paulson, Douglas N.; Allen, Paul C.

1983-01-01

A Malone-type final stage for utilization in a Stirling cycle cryogenic cooler apparatus includes a displacer slidable within a vessel. .sup.4 He, .sup.3 He, or a mixture thereof is made to flow in a pulsating unidirectional manner through a regenerator in the displacer by utilization of check valves in separate fluid channels. Stacked copper screen members extend through the channels and through a second static thermodynamic medium within the displacer to provide efficient lateral heat exchange and enable cooling to temperatures in the range of 3-4 K. Another embodiment utilizes sintered copper particles in the regenerator. Also described is a final stage that has a non-thermally conducting displacer having passages with check valves for directing fluid past a regenerator formed in the surrounding vessel.

Characterization of the basic charge variants of a human IgG1: effect of copper concentration in cell culture media.

PubMed

Kaschak, Timothy; Boyd, Daniel; Lu, Franklin; Derfus, Gayle; Kluck, Brian; Nogal, Bartek; Emery, Craig; Summers, Christie; Zheng, Kai; Bayer, Robert; Amanullah, Ashraf; Yan, Boxu

2011-01-01

We report a case study of an IgG1 with a unique basic charge variant profile caused by C-terminal proline amidation on either one or two heavy chains. The proline amidation was sensitive to copper ion concentration in the production media during cell culture: the higher the Cu ( 2+) ion concentration, the higher the level of proline amidation detected. This conclusion was supported by the analysis of samples that revealed direct correlation between the proline amidation level observed from peptide maps and the level of basic peaks measured by imaged capillary isoelectric focusing and a pH gradient ion-exchange chromatography method. The importance of these observations to therapeutic antibody production is discussed.

METHOD OF REMOVING RADIOACTIVE IODINE FROM GASES

DOEpatents

Silverman, L.

1962-01-23

A method of removing radioactive iodine from a gaseous medium is given in which the gaseous medium is adjusted to a temperature not exceeding 400 deg C and then passed over a copper fibrous pad having a coating of cupric sulfide deposited thereon. An ionic exchange on the pad results in the formation of cupric iodide and the release of sulfur. (AEC)

CuC1 thermochemical cycle for hydrogen production

DOEpatents

Fan, Qinbai [Chicago, IL; Liu, Renxuan [Chicago, IL

2012-01-03

An electrochemical cell for producing copper having a dense graphite anode electrode and a dense graphite cathode electrode disposed in a CuCl solution. An anion exchange membrane made of poly(ethylene vinyl alcohol) and polyethylenimine cross-linked with a cross-linking agent selected from the group consisting of acetone, formaldehyde, glyoxal, glutaraldehyde, and mixtures thereof is disposed between the two electrodes.

Localization via exchange splitting in NaFe1-xCuxAs

NASA Astrophysics Data System (ADS)

Charnukha, Aliaksei; Yin, Zhiping; Song, Yu; Cao, Chongde; Dai, Pengcheng; Basov, Dimitri

Iron-based high-temperature superconductors have emerged as a distinct material family believed to bridge the wide gap in understanding between conventional low-temperature and unconventional high-temperature copper-based superconductors. And yet, compounds that bear close resemblance to strongly correlated superconducting cuprates have been hard to come by. Recently, copper substitution in a quintessential iron pnictide, NaFeAs, has been demonstrated to result in a semiconducting transport behavior, suggesting the possibility of a strongly correlated Mott insulating electronic state. Here we use optical spectroscopy and dynamical mean-field theory to demonstrate explicitly that the excitation spectrum of NaFe0.5Cu0.5As possesses a sizable gap below the Neel temperature and remains unchanged up to room temperature due to the persistence of short-range antiferromagnetic correlations. We show that all of the observed experimental properties can be explained remarkably well as a result of exchange splitting in the predominantly Fe- d-derived electronic band structure induced by local antiferromagnetic order. On-site repulsion, on the contrary, is insufficient to drive localization. Our results paint a fuller picture of the intermediate character of correlations in iron-pnictides.

Deposition of ultra thin CuInS₂ absorber layers by ALD for thin film solar cells at low temperature (down to 150 °C).

PubMed

Schneider, Nathanaelle; Bouttemy, Muriel; Genevée, Pascal; Lincot, Daniel; Donsanti, Frédérique

2015-02-06

Two new processes for the atomic layer deposition of copper indium sulfide (CuInS₂) based on the use of two different sets of precursors are reported. Metal chloride precursors (CuCl, InCl₃) in combination with H2S imply relatively high deposition temperature (Tdep = 380 °C), and due to exchange reactions, CuInS₂ stoechiometry was only achieved by depositing In₂S3 layers on a CuxS film. However, the use of acac- metal precursors (Cu(acac)₂, In(acac)₃) allows the direct deposition of CuInS₂ at temperature as low as 150 °C, involving in situ copper-reduction, exchange reaction and diffusion processes. The morphology, crystallographic structure, chemical composition and optical band gap of thin films were investigated using scanning electronic microscope, x-ray diffraction under grazing incidence conditions, x-ray fluorescence, energy dispersive spectrometry, secondary ion mass spectrometry, x-ray photoelectron spectroscopy and UV-vis spectroscopy. Films were implemented as ultra-thin absorbers in a typical CIS-solar cell architecture and allowed conversion efficiencies up to 2.8%.

Dilution Refrigerator for Nuclear Refrigeration and Cryogenic Thermometry Studies

NASA Astrophysics Data System (ADS)

Nakagawa, Hisashi; Hata, Tohru

2014-07-01

This study explores the design and construction of an ultra-low temperature facility in order to realize the Provisional low-temperature scale from 0.9 mK to 1 K (PLTS-2000) in Japan, to disseminate its use through calibration services, and to study thermometry at low temperatures below 1 K. To this end, a dilution refrigerator was constructed in-house that has four sintered silver discrete heat exchangers for use as a precooling stage of a copper nuclear demagnetization stage. A melting curve thermometer attached to the mixing chamber flange could be cooled continuously to 4.0 mK using the refrigerator. The dependence of minimum temperatures on circulation rates can be explained by the calculation of Frossati's formula based on a perfect continuous counterflow heat exchanger model, assuming that the Kapitza resistance has a temperature dependence. Residual heat leakage to the mixing chamber was estimated to be around 86 nW. A nuclear demagnetization cryostat with a nuclear stage containing an effective amount of copper (51 mol in a 9 T magnetic field) is under construction, and we will presently start to work toward the realization of the PLTS-2000. In this article, the design and performance of the dilution refrigerator are reported.

Investigation of stand-off distance effect on structure, adhesion and hardness of copper coatings obtained by the APS technique

NASA Astrophysics Data System (ADS)

Masoumeh, Goudarzi; Shahrooz, Saviz; Mahmood, Ghoranneviss; Ahmad, Salar Elahi

2018-03-01

The outbreak of the disease and infection in the hospital environment and medical equipment is one of the concerns of modern life. One of the effective ways for preventing and reducing the complications of infections is modification of the surface. Here, the handmade atmospheric plasma spray system is used for accumulating copper as an antibacterial agent on the 316L stainless steel substrate, which applies to hospital environment and medical equipment. As a durable coating with proper adhesion is needed on the substrate, the effect of stand-off distance (SOD) which is an important parameter of the spray on the microstructure, the hardness and adhesion of the copper coating on the 316L stainless steel were investigated. The structure and phase composition of copper depositions were investigated using scanning electron microscopy and X-ray diffraction. The adhesion and hardness of depositions are evidenced using the cross cut tester and Vickers hardness tester, respectively. The findings confirm that the voids in the coatings increase with increasing SOD, which leads to decreasing the hardness of coatings and also the adhesion strength between depositions and substrate. In addition, by increasing the SOD, the oxygen content and the size of grains in the lamellae (fine structure) of coatings also increase.

Synthesis of Cross-Linked Polymeric Micelle pH Nanosensors: An Investigation of Design Flexibility.

PubMed

Kumar, E K Pramod; Jølck, Rasmus I; Andresen, Thomas L

2015-09-01

The design flexibility that polymeric micelles offer in the fabrication of optical nanosensors for ratiometric pH measurements is investigated. pH nanosensors based on polymeric micelles are synthesized either by a mixed-micellization approach or by a postmicelle modification strategy. In the mixed-micellization approach, self-assembly of functionalized unimers followed by shell cross-linking by copper-catalyzed azide-alkyne cycloaddition (CuAAC) results in stabilized cRGD-functionalized micelle pH nanosensors. In the postmicelle modification strategy, simultaneous cross-linking and fluorophore conjugation at the micelle shell using CuAAC results in a stabilized micelle pH nanosensor. Compared to the postmicelle modification strategy, the mixed-micellization approach increases the control of the overall composition of the nanosensors. Both approaches provide stable nanosensors with similar pKa profiles and thereby nanosensors with similar pH sensitivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and microwave modification of CuO nanoparticles: crystallinity and morphological variations, catalysis, and gas sensing.

PubMed

Yang, Chao; Xiao, Feng; Wang, Jide; Su, Xintai

2014-12-01

CuO nanoparticles with different morphologies were synthesized by chemical precipitation and subsequently modified by microwave hydrothermal processing. The nanoparticles were precipitated by the introduction of a strong base to an aqueous solution of copper cations in the presence/absence of the polyethylene glycol and urea additives. The modification of the nanoparticles was subsequently carried out by a microwave hydrothermal treatment of suspensions of the precipitates, precipitated with and without the additives. X-ray powder diffraction analysis indicated that the crystallinity and crystallite size of the CuO nanoparticles increased after the microwave hydrothermal modification. Microscopy observations revealed the morphology changes induced by microwave hydrothermal processing. The thermal decomposition of ammonium perchlorate and the detection of volatile gases were performed to evaluate the catalytic and gas sensing properties of the synthesized CuO nanoparticles. Copyright © 2014 Elsevier Inc. All rights reserved.

Single- and multi-pulse formation of surface structures under static femtosecond irradiation

NASA Astrophysics Data System (ADS)

Guillermin, M.; Garrelie, F.; Sanner, N.; Audouard, E.; Soder, H.

2007-07-01

Femtosecond surface structure modifications are investigated under irradiation with laser pulses of 150 fs at 800 nm, on copper and silicon. We report sub-wavelength periodic structures formation (ripples) with a periodicity of 500 nm for both materials. These ripples are perpendicular to the laser polarization and can be obtained with only one pulse. The formation of these ripples corresponds to a fluence threshold of 1 J/cm 2 for copper and 0.15 J/cm 2 for silicon. We find several morphologies when more pulses are applied: larger ripples parallel to the polarization are formed with a periodicity of 1 μm and degenerate into a worm-like morphology with a higher number of pulses. In addition, walls of deep holes also show sub-wavelength and large ripples.

[The change in optical spectra from solid and liquid solution of copper phthalocyanines derivatives].

PubMed

Zheng, Xiao-pan; He, Zhi-qun; Zhang, Chun-xiu; Xu, Zheng; Wang, Yong-sheng

2006-06-01

In the present work, the change in electronic absorption spectra from three copper phthalocyanines (CuPc, tb-CuPc, oo-CuPc) in different environments was investigated. The mechanism of red shift Q-band absorption from the three species in an organic solvent before and after protonation was discussed. This was used to compare with those dispersed in solid films. The relation between the molecular interactions and the spectra change was studied. In a combination of POM, DSC and XRD techniques, the structure and morphology of the thin films were characterised. It was found that the molecules in the doped matrices of PC were associated or aggregated. This association and hence the corresponding change in absorption spectra cannot be altered by the modification of dopant concentration.

Influence of Nano-Fluid and Receiver Modification in Solar Parabolic Trough Collector Performance

NASA Astrophysics Data System (ADS)

Dharani Kumar, M.; Yuvaraj, G.; Balaji, D.; Pravinraj, R.; shanmugasundaram, Prabhu

2018-02-01

Utilization of natural renewal sources in India is very high over the past decades. Solar power is a prime source of energy available plenty in the world. In this work solar energy is modified into thermal energy by using copper absorber tube with fins. Due to low heat transfer coefficient results leading to higher thermal losses and lower thermal efficiency. In order to increase the heat transfer coefficient copper receiver tube with fins is used and as well as solid has higher thermal conductivity compare to fluid (Tio2) nano fluid is used to improve the heat transfer rate. The analyses have been carried out and take the account of parameters such as solar radiation with time variation, mass flow rate of water, temperatures.

A new approach for crystallization of copper(ii) oxide hollow nanostructures with superior catalytic and magnetic response

NASA Astrophysics Data System (ADS)

Singh, Inderjeet; Landfester, Katharina; Chandra, Amreesh; Muñoz-Espí, Rafael

2015-11-01

We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism.We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism. Electronic supplementary information (ESI) available: Associated structural and morphological analysis, XPS characterization, BET surface area, catalytic measurements, recycle tests of the catalyst, and magnetic characterizations. See DOI: 10.1039/c5nr05579b

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, Lane A.; Ryan, Jack L.

1999-01-01

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the 22.sup.9 Th or 2.sup.27 Ac "cow" radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium; lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture; are removed from the mixture on the chloride form anion exchange column.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, L.A.; Ryan, J.L.

1999-03-23

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the {sup 229}Th or {sup 227}Ac ``cow`` radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium, lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture are removed from the mixture on the chloride form anion exchange column. 8 figs.

Anion permselective membrane

NASA Technical Reports Server (NTRS)

Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

1984-01-01

Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

Relational Contract: Applicable to Department of Defense Contracts

DTIC Science & Technology

1989-12-01

examine the evolution of contract law and, in particular, the role of contractual incompleteness in exchange relationships. 2.1.1. The Classical Approach...Classical contract law facilitates exchange by separately detailing all aspects of the contracting process 9 at the outset by prespecification of all...modifications after contractual performance has begun. According to Williamson (1979), classical contract law implements prespecification through legal

High Temperature Thermosetting Polyimide Nanocomposites Prepared with Reduced Charge Organoclay

NASA Technical Reports Server (NTRS)

Campbell, Sandi; Liang, Margaret I.

2005-01-01

The naturally occurring sodium and calcium cations found in bentonite clay galleries were exchanged with lithium cations. Following the cation exchange, a series of reduced charge clays were prepared by heat treatment of the lithium bentonite at 130 C, 150 C, or 170 C. Inductively coupled plasma (ICP) analysis showed that heating the lithium clay at elevated temperatures reduced its cation exchange capacity. Ion exchange of heat-treated clays with either a protonated alkyl amine or a protonated aromatic diamine resulted in decreasing amounts of the organic modifier incorporated into the lithium clay. The level of silicate dispersion in a thermosetting polyimide matrix was dependent upon the temperature of Li-clay heat treatment as well as the organic modification. In general, clays treated at 150 C or 170 C, and exchanged with protonated octadcylamine or protonated 2,2'-dimethlybenzidine (DMBZ) showed a higher degree of dispersion than clays treated at 130 C, or exchanged with protonated dodecylamine. Dynamic mechanical analysis showed little change in the storage modulus or T(sub g) of the nanocomposites compared to the base resin. However, long term isothermal aging of the samples showed a significant decrease in the resin oxidative weight loss. Nanocomposite samples aged in air for 1000 hours at 288 C showed of to a decrease in weight loss compared to that of the base resin. This again was dependent on the temperature at which the Li-clay was heated and the choice of organic modification.

Mesoporous TiO2 and copper-modified TiO2 nanoparticles: A case study

NASA Astrophysics Data System (ADS)

Ajay Kumar, R.; Vasavi Dutt, V. G.; Rajesh, Ch.

2018-02-01

In this paper we report the synthesis of mesoporous titanium dioxide (M-TiO2) nanoparticles (NPs) and copper (Cu)-modified M-TiO2 NPs by the hydrothermal method at relatively low temperatures using cetyltrimethylammonium bromide (CTAB) as a template. In order to get ordered spherical particles and better interaction between cationic and anionic precursor, we have used titanium isopropoxide (TTIP) as titanium source and CTAB as surfactant. The process of modification by copper to M-TiO2 follows the impregnation method. The change in structural and optical properties of NPs were estimated using different characterization techniques like X-ray diffraction, field emission scanning electron microscopy, Brunner-Emmett-Teller curve and UV-Vis absorption analysis. M-TiO2 and Cu-modified M-TiO2 exhibit pure anatase crystalline phase and shows no evidence of CuO formation. Nitrogen adsorption-desorption hysteresis reveals that the material is mesoporous. Several samples synthesized at different process temperature were further studied in order to make them suitable for a wide range of applications.

Modeling of breakdown during the post-arc phase of a vacuum circuit breaker

NASA Astrophysics Data System (ADS)

Sarrailh, P.; Garrigues, L.; Boeuf, J. P.; Hagelaar, G. J. M.

2010-12-01

After a high-current interruption in a vacuum circuit breaker (VCB), the electrode gap is filled with a high density copper vapor plasma in a large copper vapor density (~1022 m-3). The copper vapor density is sustained by electrode evaporation. During the post-arc phase, a rapidly increasing voltage is applied to the gap, and a sheath forms and expands, expelling the plasma from the gap when circuit breaking is successful. There is, however, a risk of breakdown during that phase, leading to the failure of the VCB. Preventing breakdown during the post-arc phase is an important issue for the improvement of VCB reliability. In this paper, we analyze the risk of Townsend breakdown in the high copper vapor density during the post-arc phase using a numerical model that takes into account secondary electron emission, volume ionization, and plasma and neutral transport, for given electrode temperatures. The simulations show that fast neutrals created in the cathode sheath by charge exchange collisions with ions generate a very large secondary electron emission current that can lead to Townsend breakdown. The results also show that the risk of failure of the VCB due to Townsend breakdown strongly depends on the electrode temperatures (which govern the copper vapor density) and becomes important for temperatures greater than 2100 K, which can be reached in vacuum arcs. The simulations also predict that a hotter anode tends to increase the risk of Townsend breakdown.

Photoluminescence of CuInS2 nanocrystals: effect of surface modification

NASA Astrophysics Data System (ADS)

Kim, Young-Kuk; Cho, Young-Sang; Chung, Kookchae; Choi, Chul-Jin

2011-09-01

We have synthesized highly luminescent Cu-In-S(CIS) nanocrystals (NCs) by heating the mixture of metal carboxylates and alkylthiol under inert atmosphere. We modified the surface of CIS NCs with zinc carboxylate and subsequent injection of alkylthiol. As a result of the surface modification, highly luminescent CIS@ZnS core/shell nanocrystals were synthesized. The luminescence quantum yield (QY) of best CIS@ZnS NCs was above 50%, which is 10 times higher than the initial QY of CIS NCs before surface modification (QY=3%). Detailed study on the luminescence mechanism implies that etching of the surface of NCs by dissociated carboxylate group (CH3COO-) and formation of epitaxial shell by Zn with sulfur from alkylthiol efficiently removed the surface defects which are known to be major non-radiative recombination sites in semiconductor nanocrystals. In this study, we developed a novel surface modification route for monodispersed highly luminescent Cu-In-S NCs with less toxic and highly stable precursors. Investigation with the timeand the temperature-dependent photoluminescence showed that the trap related emission was minimized by surface modification and the donor-acceptor pair recombination was enhanced by controlling copper stoichiometry.xb

77 FR 75464 - Order Granting Limited Exemptions From Exchange Act Rules 101 and 102 of Regulation M to Shares...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-20

... agent,\\6\\ and information transparency measures \\7\\ will cause the price of Shares in the secondary... price of Shares is expected to trade within a limited range with the lower end of that range... align the price of the Shares in the secondary market to the copper held by the Trust, should mitigate...

Identification of copper phthalocyanine blue polymorphs in unaged and aged paint systems by means of micro-Raman spectroscopy and Random Forest.

PubMed

Anghelone, Marta; Jembrih-Simbürger, Dubravka; Schreiner, Manfred

2015-10-05

Copper phthalocyanine (CuPc) blues (PB15) are largely used in art and industry as pigments. In these fields mainly three different polymorphic modifications of PB15 are employed: alpha, beta and epsilon. Differentiating among these CuPc forms can give important information for developing conservation strategy and can help in relative dating, since each form was introduced in the market in different time periods. This study focuses on the classification of Raman spectra measured using 532 nm excitation wavelength on: (i) dry pigment powders, (ii) unaged mock-ups of self-made paints, (iii) unaged commercial paints, and (iv) paints subjected to accelerated UV ageing. The ratios among integrated Raman bands are taken in consideration as features to perform Random Forest (RF). Features selection based on Gini Contrast score was carried out on the measured dataset to determine the Raman bands ratios with higher predictive power. These were used as polymorphic markers, in order to establish an easy and accessible method for the identification. Three different ratios and the presence of a characteristic vibrational band allowed the identification of the crystal modification in pigments powder as well as in unaged and aged paint films. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-09-20

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Ohno continuous casting

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

Soda, H.; McLean, A.; Motoyasu, G.

1995-04-01

Production of net-shape products directly from the liquid is an attractive manufacturing route for alloys that are difficult to process or that cannot be rolled, drawn, or extruded. Developed at the Chiba Institute of Technology in Japan, the Ohno Continuous Casting (OCC) approach not only provides significant cost savings, but also has the potential to create new products. OCC process equipment includes a melting furnace, crucible, mold level-control block, cooling device, and pinch rolls. OCC is currently used to produce copper rods and wires for audio and video cables, and aluminum alloy welding rods for hard-surfacing applications. For example, Mitsuimore » Engineering and Ship Building Co. has used OCC to produce copper tubing products with internal fins and partitions for applications such as heat exchanger tubes and induction coils.« less

Palladium Coated Copper Nanowires as a Hydrogen Oxidation Electrocatalyst in Base

DOE PAGES

Alia, Shaun M.; Yan, Yushan

2015-05-09

The palladium (Pd) nanotubes we synthesized by the spontaneous galvanic displacement of copper (Cu) nanowires, are forming extended surface nanostructures highly active for the hydrogen oxidation reaction (HOR) in base. The synthesized catalysts produce specific activities in rotating disk electrode half-cells 20 times greater than Pd nanoparticles and about 80% higher than polycrystalline Pd. Although the surface area of the Pd nanotubes was low compared to conventional catalysts, partial galvanic displacement thrifted the noble metal layer and increased the Pd surface area. Moreover, the use of Pd coated Cu nanowires resulted in a HOR mass exchange current density 7 timesmore » greater than the Pd nanoparticles. The activity of the Pd coated Cu nanowires further nears Pt/C, producing 95% of the mass activity.« less

From the Chemistry Lab to Licensing

NASA Technical Reports Server (NTRS)

Savino, Joseph M.; Street, Kenneth W.; Philipp, Warren H.

1998-01-01

This is a story of technology maturation and transfer, and licensing. It traces the history of the recently patented ion- exchange material (IEM) from the accidental discovery that this polymer, a battery separator of marginal performance, picked up copper from distilled water passing through corroded copper tubing in the laboratory, to a point where five organizations and one individual have applied for licenses to manufacture and market it or to use it in a wide variety of applications. This story discusses in detail the problems of converting an immature technology into a mature and eventually commercialized technology, without dedicated resources. Readers will develop an appreciation for how the obstacles to maturation and licensing of the technology were faced and overcome. The lessons learned will be discussed, with the hope of enhancing the technology transfer process.

Acceptability of randomization to levonorgestrel versus copper intrauterine device among women requesting IUD insertion for contraception

PubMed Central

Achilles, Sharon L.; Chen, Beatrice A.; Lee, Jessica K.; Gariepy, Aileen M.; Creinin, Mitchell D.

2015-01-01

Objective Assess feasibility of randomizing women to intrauterine device (IUD) type. Study Design Women enrolling in a 2-month study who desired an IUD for contraception were randomized 1:1 to receive a levonorgestrel 52mg IUD (LNG-IUD) or copper T380A (Cu-IUD), understanding they could switch IUD type at the end of the study. Results Randomization to IUD type was acceptable to 54/55 (98%) women who screened. All 32 enrolled participants completed follow-up. Two women exchanged their IUD (Cu-IUD to LNG-IUD) and 2 requested removal (1 LNG-IUD, 1 Cu-IUD). Overall, 88% continued their assigned IUD. Conclusions Randomization to IUD type is feasible and few women change their IUD. PMID:26297203

Friction Stir Processing of Particle Reinforced Composite Materials

PubMed Central

Gan, Yong X.; Solomon, Daniel; Reinbolt, Michael

2010-01-01

The objective of this article is to provide a review of friction stir processing (FSP) technology and its application for microstructure modification of particle reinforced composite materials. The main focus of FSP was on aluminum based alloys and composites. Recently, many researchers have investigated this technology for treating other alloys and materials including stainless steels, magnesium, titanium, and copper. It is shown that FSP technology is very effective in microstructure modification of reinforced metal matrix composite materials. FSP has also been used in the processing and structure modification of polymeric composite materials. Compared with other manufacturing processes, friction stir processing has the advantage of reducing distortion and defects in materials. The layout of this paper is as follows. The friction stir processing technology will be presented first. Then, the application of this technology in manufacturing and structure modification of particle reinforced composite materials will be introduced. Future application of friction stir processing in energy field, for example, for vanadium alloy and composites will be discussed. Finally, the challenges for improving friction stir processing technology will be mentioned.

Polymeric networks of copper(II) phenylmalonate with heteroaromatic n-donor ligands: synthesis, crystal structure, and magnetic properties.

PubMed

Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel

2005-10-31

Two new phenylmalonate-bridged copper(II) complexes with the formulas [Cu(4,4'-bpy)(Phmal)](n).2nH(2)O (1) and [Cu(2,4'-bpy)(Phmal)(H(2)O)](n)() (2) (Phmal = phenylmalonate dianion, 4,4'-bpy = 4,4'-bipyridine, 2,4'-bpy = 2,4'-bipyridine) have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in monoclinic space group P2(1), Z = 4, with unit cell parameters of a = 9.0837(6) Angstroms, b = 9.3514(4) Angstroms, c = 11.0831(8) Angstroms, and beta = 107.807(6) degrees , whereas complex 2 crystallizes in orthorhombic space group C2cb, Z = 8, with unit cell parameters of a = 10.1579(7) Angstroms, b = 10.3640(8) Angstroms, and c = 33.313(4) Angstroms. The structures of 1 and 2 consist of layers of copper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4'-bpy (1) ligands and terminal monodentate 2,4'-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08 x 4.99 Angstroms(2), the edges being defined by the Phmal and 4,4'-bpy ligands. The intralayer copper-copper separations in 1 through the anti-syn equatorial-apical carboxylate-bridge and the 4,4'-bpy molecule are 4.9922(4) and 11.083(1) Angstroms, respectively. The anti-syn equatorial-equatorial carboxylate bridge links the copper(II) atoms in complex 2 within each layer with a mean copper-copper separation of 5.3709(8) Angstroms. The presence of 2,4'-bpy as a terminal ligand accounts for the large interlayer separation of 15.22 Angstroms. The copper(II) environment presents a static pseudo-Jahn-Teller disorder which has been studied by EPR and low-temperature X-ray diffraction. Magnetic susceptibility measurements of both compounds in the temperature range 2-290 K show the occurrence of weak antiferromagnetic [J = -0.59(1) cm(-1) (1)] and ferromagnetic [J = +0.77(1) cm(-1) (2)] interactions between the copper(II) ions. The conformation of the phenylmalonate-carboxylate bridge and other structural factors, such as the planarity of the exchange pathway in 1, account for the different nature of the magnetic interaction.

Recombinase-Mediated Cassette Exchange Using Adenoviral Vectors.

PubMed

Kolb, Andreas F; Knowles, Christopher; Pultinevicius, Patrikas; Harbottle, Jennifer A; Petrie, Linda; Robinson, Claire; Sorrell, David A

2017-01-01

Site-specific recombinases are important tools for the modification of mammalian genomes. In conjunction with viral vectors, they can be utilized to mediate site-specific gene insertions in animals and in cell lines which are difficult to transfect. Here we describe a method for the generation and analysis of an adenovirus vector supporting a recombinase-mediated cassette exchange reaction and discuss the advantages and limitations of this approach.

Boiling on Microconfigured Composite Surfaces Enhanced

NASA Technical Reports Server (NTRS)

Chao, David F.

2000-01-01

Boiling heat transfer is one of the key technologies for the two-phase active thermal-control system used on space platforms, as well as for the dynamic power systems aboard the International Space Station. Because it is an effective heat transfer mode, boiling is integral to many space applications, such as heat exchangers and other cooling devices. Nucleate boiling near the critical heat flux (CHF) can transport very large thermal loads with a much smaller device and much lower pumping power than for single-phase heat exchangers. However, boiling performance sharply deteriorates in a reduced-gravity environment, and operation in the CHF regime is somewhat perilous because of the risk of burnout to the device surface. New materials called microconfigured metal-graphite composites can enhance boiling. The photomicrograph shows the microconfiguration (x3000) of the copper-graphite (Cu-Gr) surface as viewed by scanning electronic microscope. The graphite fiber tips appear as plateaus with rugged surfaces embedded in the copper matrix. It has been experimentally demonstrated that this type of material manifests excellent boiling heat transfer performance characteristics and an increased CHF. Nonisothermal surfaces were less sensitive to variations of wall superheat in the CHF regime. Because of the great difference in conductivity between the copper base and the graphite fiber, the composite surfaces have a nonisothermal surface characteristic and, therefore, will have a much larger "safe" operating region in the CHF regime. In addition, the thermocapillary forces induced by the temperature differences between the fiber tips and the metal matrix play an important role in bubble detachment, and may not be adversely affected in a reduced-gravity environment. All these factors indicate that microconfigured composites may improve the reliability and economy (dominant factors in all space applications) of various thermal components found on spacecraft during future missions.

Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

NASA Astrophysics Data System (ADS)

Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

2013-06-01

Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

Properties of hydrocarbon- and salt-contaminated flare pit soils in northeastern British Columbia (Canada).

PubMed

Arocena, J M; Rutherford, P M

2005-07-01

Many contaminated sites in Canada are associated with flare pits generated during past petroleum extraction operations. Flare pits are located adjacent to well sites, compressor stations and batteries and are often subjected to the disposal of wastes from the flaring of gas, liquid hydrocarbons and brine water. This study was conducted to evaluate the physical, chemical, electrical and mineral properties of three flare pit soils as compared to adjacent control soils. Results showed that particle size distribution, pH, total N, cation exchange capacity, exchangeable Mg(2+), and sodium adsorption ratio were similar in soils from flare pits and control sites. Total C, exchangeable Ca(2+), K(+) and Na(+), soluble Ca(2+), Mg(2+), K(+) and Na(+) and electrical conductivity were higher in flare pit soils compared to control soils. X-ray diffraction and scanning electron microscopic analyses showed the presence of gypsum [CaSO(4).2H(2)O], dolomite [CaMg(CO(3))(2)], pyrite [FeS(2)], jarosite [KFe(3)(OH)(6)(SO(4))(2)], magnesium sulphate, oxides of copper and iron+copper in salt efflorescence observed in flare pit soils. Soils from both flare pits and control sites contained mica, kaolonite and 2:1 expanding clays. The salt-rich materials altered the ionic equilibria in the flare pit soils; K(Mg-Ca) selectivity coefficients in control soils were higher compared to contaminated soils. The properties of soils (e.g., high electrical conductivity) affected by inputs associated with oil and gas operations might render flare pit soils less conducive to the establishment and growth of common agricultural crops and forest trees.

Modification of chemical properties, Cu fractionation and enzymatic activities in an acid vineyard soil amended with winery wastes: A field study.

PubMed

Rodríguez-Salgado, Isabel; Pérez-Rodríguez, Paula; Gómez-Armesto, Antía; Díaz-Raviña, Montserrat; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel; Fernández-Calviño, David

2017-11-01

The effects of adding two winery wastes, perlite waste (PW) and bentonite waste (BW), to an acid vineyard soil were assessed using some chemical and biological soil properties in a field study that lasted 18 months. The addition of PW (up to 81 Mg ha -1 ) had neither significant nor permanent effects on soil characteristics such as the pH, organic matter content or nutrient concentrations, the amounts of copper or zinc, or the electrical conductivity. Moreover, no persistent negative effects were found on the enzymatic activities after PW application. In contrast, soil that was amended with up to 71 Mg BW ha -1 showed increases in its soil pH values, exchangeable potassium and water soluble potassium and phosphorus contents. In addition, it caused significant increases in the electrical conductivity and water-soluble Cu. In addition, the phosphomonoesterase enzymatic activity decreased significantly (up to 28%) in response to the amendment with 71 Mg BW ha -1 . These results showed that adding BW and PW to the soil may be a good agronomic practice for recycling these types of wastes. However, in the case of PW, its use as a soil amendment must be performed with caution to control its possible harmful effects. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of Additives on Electrochemical Growth of Cu Film on Co/SiO2/Si Substrate by Alternating Underpotential Deposition of Pb and Surface-Limited Redox Replacement by Cu

NASA Astrophysics Data System (ADS)

Fang, J. S.; Lin, L. Y.; Wu, C. L.; Cheng, Y. L.; Chen, G. S.

2017-11-01

The effects of additives to an acidic electrolyte for electrochemical deposition of copper film to prevent corrosion of the Co/SiO2/Si substrate have been investigated. A sacrificial Pb layer was formed by underpotential deposition (UPD), then a Cu layer was prepared using surface-limited redox replacement (SLRR) to exchange the UPD-Pb layer in an acidic copper electrolyte with trisodium citrate, sodium perchlorate, and ethylenediamine as additives. The additives significantly affected the replacement of UPD-Pb by Cu and prevented galvanic corrosion of the Co/SiO2/Si substrate in the acidic Cu electrolyte. The results showed that both sodium perchlorate and ethylenediamine reduced the corrosion of the Co substrate and resulted in Cu film with low electrical resistivity. However, residual Pb was present in the Cu film when using trisodium citrate, as the citrate ions slowed copper displacement. The proposed sequential UPD-Pb and SLRR-Cu growth method may enable electrochemical deposition for fabrication of Cu interconnects on Co substrate from acidic Cu electrolyte.

Power module packaging with double sided planar interconnection and heat exchangers

DOEpatents

Liang, Zhenxian; Marlino, Laura D.; Ning, Puqi; Wang, Fei

2015-05-26

A double sided cooled power module package having a single phase leg topology includes two IGBT and two diode semiconductor dies. Each IGBT die is spaced apart from a diode semiconductor die, forming a switch unit. Two switch units are placed in a planar face-up and face-down configuration. A pair of DBC or other insulated metallic substrates is affixed to each side of the planar phase leg semiconductor dies to form a sandwich structure. Attachment layers are disposed on outer surfaces of the substrates and two heat exchangers are affixed to the substrates by rigid bond layers. The heat exchangers, made of copper or aluminum, have passages for carrying coolant. The power package is manufactured in a two-step assembly and heating process where direct bonds are formed for all bond layers by soldering, sintering, solid diffusion bonding or transient liquid diffusion bonding, with a specially designed jig and fixture.

Tetrabutylammonium-modified clay film electrodes: characterization and application to the detection of metal ions.

PubMed

Maghear, Adela; Tertiş, Mihaela; Fritea, Luminţa; Marian, Iuliu O; Indrea, Emil; Walcarius, Alain; Săndulescu, Robert

2014-07-01

This work describes the preparation and characterization of smectite clay partially exchanged with tetrabutylammonium ions (TBA(+)) and its subsequent deposition onto glassy carbon electrode (GCE) for application to the preconcentration electroanalysis of metal ions (Cd, Pb, and Cu). Such partial exchange of TBA(+) induces the expansion of the interlayer region between the clay sheets (as ascertained by XRD) while maintaining its ion exchange capacity, which resulted in enhanced mass transport rates (as pointed out by electrochemical monitoring of permeability properties of these thin (organo)clay films on GCE). This principle was applied here to the anodic stripping square wave voltammetric analysis of metal ions after accumulation at open circuit. Among others, detection limits as low as 3.6×10(-8)M for copper and 7.2×10(-8)M for cadmium have been achieved. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Korolev, D.A.; Zhuk, N.A.

On the basis of the results of magnetic susceptibility and ESR studies of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions iron atoms in the solid solutions of cubic modification of bismuth niobate were found to exist as Fe(III) monomers and exchange bound Fe(III)-O-Fe(III) dimers with antiferro- and ferromagnetic type of superexchange. The exchange parameters and the distribution of monomers and dimers in the solid solutions were calculated as a function of paramagnetic atom content. - Graphical abstract: The study of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions showed that the introduction of iron atoms into the structure ofmore » Bi{sub 3}NbO{sub 7} stabilizes the cubic structure of bismuth niobate making the phase transition tetragonal ↔ cubic structure irreversible. In the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions we observe the formation of dimers with antiferro- and ferromagnetic exchange. Such clusters are partially retained even at the infinite dilution of the solid solution, which testifies for their rigidity. A sufficiently high parameter of ferromagnetic exchange in a dimer (+53 cm{sup −1}) seems to result from iron atoms being located in the vicinity of oxygen vacancy. - Highlights: • The reversible transition cubic – tetragonal modifications in Bi{sub 3}NbO{sub 7} becomes irreversible. • Only cubic modification of Bi{sub 3}Nb{sub 1-x}Fe{sub x}O{sub 7-δ} is stable due to clusters of Fe atoms. • These clusters are sufficiently strong and retained even at the infinite dilution. • The calculations of magnetic susceptibility give the distribution of the clusters and single atoms.« less

Distinct oxidative cleavage and modification of bovine [Cu-Zn]-SOD by an ascorbic acid/Cu(II) system: Identification of novel copper binding site on SOD molecule

PubMed Central

Uehara, Hiroshi; Luo, Shen; Aryal, Baikuntha; Levine, Rodney L.; Rao, V. Ashutosh

2016-01-01

We investigated the combined effect of ascorbate and copper [Asc/Cu(II)] on the integrity of bovine [Cu-Zn]-superoxide dismutase (bSOD1) as a model system to study the metal catalyzed oxidation (MCO) and fragmentation of proteins. We found Asc/Cu(II) mediates specific cleavage of bSOD1 and generates 12.5 and 3.2 kDa fragments in addition to oxidation/carbonylation of the protein. The effect of other tested transition metals, a metal chelator, and hydrogen peroxide on the cleavage and oxidation indicated that binding of copper to a previously unknown site on SOD1 is responsible for the Asc/Cu(II) specific cleavage and oxidation. We utilized tandem mass spectrometry to identify the specific cleavage sites of Asc/Cu(II)-treated bSOD1. Analyses of tryptic- and AspN-peptides have demonstrated the cleavage to occur at Gly31 with peptide bond breakage with Thr30 and Ser32 through diamide and α-amidation pathways, respectively. The three-dimensional structure of bSOD1 reveals the imidazole ring of His19 localized within 5 Angstrom from the α-carbon of Gly31 providing a structural basis that copper ion, most likely coordinated by His19, catalyzes the specific cleavage reaction. PMID:26872685

Distinct oxidative cleavage and modification of bovine [Cu- Zn]-SOD by an ascorbic acid/Cu(II) system: Identification of novel copper binding site on SOD molecule.

PubMed

Uehara, Hiroshi; Luo, Shen; Aryal, Baikuntha; Levine, Rodney L; Rao, V Ashutosh

2016-05-01

We investigated the combined effect of ascorbate and copper [Asc/Cu(II)] on the integrity of bovine [Cu-Zn]-superoxide dismutase (bSOD1) as a model system to study the metal catalyzed oxidation (MCO) and fragmentation of proteins. We found Asc/Cu(II) mediates specific cleavage of bSOD1 and generates 12.5 and 3.2kDa fragments in addition to oxidation/carbonylation of the protein. The effect of other tested transition metals, a metal chelator, and hydrogen peroxide on the cleavage and oxidation indicated that binding of copper to a previously unknown site on SOD1 is responsible for the Asc/Cu(II) specific cleavage and oxidation. We utilized tandem mass spectrometry to identify the specific cleavage sites of Asc/Cu(II)-treated bSOD1. Analyses of tryptic- and AspN-peptides have demonstrated the cleavage to occur at Gly31 with peptide bond breakage with Thr30 and Ser32 through diamide and α-amidation pathways, respectively. The three-dimensional structure of bSOD1 reveals the imidazole ring of His19 localized within 5Å from the α-carbon of Gly31 providing a structural basis that copper ion, most likely coordinated by His19, catalyzes the specific cleavage reaction. Published by Elsevier Inc.

Cre/lox-Recombinase-Mediated Cassette Exchange for Reversible Site-Specific Genomic Targeting of the Disease Vector, Aedes aegypti.

PubMed

Häcker, Irina; Harrell Ii, Robert A; Eichner, Gerrit; Pilitt, Kristina L; O'Brochta, David A; Handler, Alfred M; Schetelig, Marc F

2017-03-07

Site-specific genome modification (SSM) is an important tool for mosquito functional genomics and comparative gene expression studies, which contribute to a better understanding of mosquito biology and are thus a key to finding new strategies to eliminate vector-borne diseases. Moreover, it allows for the creation of advanced transgenic strains for vector control programs. SSM circumvents the drawbacks of transposon-mediated transgenesis, where random transgene integration into the host genome results in insertional mutagenesis and variable position effects. We applied the Cre/lox recombinase-mediated cassette exchange (RMCE) system to Aedes aegypti, the vector of dengue, chikungunya, and Zika viruses. In this context we created four target site lines for RMCE and evaluated their fitness costs. Cre-RMCE is functional in a two-step mechanism and with good efficiency in Ae. aegypti. The advantages of Cre-RMCE over existing site-specific modification systems for Ae. aegypti, phiC31-RMCE and CRISPR, originate in the preservation of the recombination sites, which 1) allows successive modifications and rapid expansion or adaptation of existing systems by repeated targeting of the same site; and 2) provides reversibility, thus allowing the excision of undesired sequences. Thereby, Cre-RMCE complements existing genomic modification tools, adding flexibility and versatility to vector genome targeting.

Extended cooperation in clinical studies through exchange of CDISC metadata between different study software solutions.

PubMed

Kuchinke, W; Wiegelmann, S; Verplancke, P; Ohmann, C

2006-01-01

Our objectives were to analyze the possibility of an exchange of an entire clinical study between two different and independent study software solutions. The question addressed was whether a software-independent transfer of study metadata can be performed without programming efforts and with software routinely used for clinical research. Study metadata was transferred with ODM standard (CDISC). Study software systems employed were MACRO (InferMed) and XTrial (XClinical). For the Proof of Concept, a test study was created with MACRO and exported as ODM. For modification and validation of the ODM export file XML-Spy (Altova) and ODM-Checker (XML4Pharma) were used. Through exchange of a complete clinical study between two different study software solutions, a Proof of Concept of the technical feasibility of a system-independent metadata exchange was conducted successfully. The interchange of study metadata between two different systems at different centers was performed with minimal expenditure. A small number of mistakes had to be corrected in order to generate a syntactically correct ODM file and a "vendor extension" had to be inserted. After these modifications, XTrial exhibited the study, including all data fields, correctly. However, the optical appearance of both CRFs (case report forms) was different. ODM can be used as an exchange format for clinical studies between different study software. Thus, new forms of cooperation through exchange of metadata seem possible, for example the joint creation of electronic study protocols or CRFs at different research centers. Although the ODM standard represents a clinical study completely, it contains no information about the representation of data fields in CRFs.

77 FR 75468 - Self-Regulatory Organizations; NYSE Arca, Inc.; Notice of Filing of Amendment No. 1 and Order...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-20

... SECURITIES AND EXCHANGE COMMISSION [Release No. 34-68440; File No. SR-NYSEArca-2012-28] Self-Regulatory Organizations; NYSE Arca, Inc.; Notice of Filing of Amendment No. 1 and Order Granting Accelerated Approval of a Proposed Rule Change as Modified by Amendment No. 1 To List and Trade Shares of the JPM XF Physical Copper Trust Pursuant to NYSE...

Bioavailability of Lead in Small Arms Range Soils

DTIC Science & Technology

2009-08-01

titanium TOC total organic carbon USEPA U.S. Environmental Protection Agency XRF X-ray fluorescence Zn zinc Zr zirconium 1 1.0 EXECUTIVE...particles of inert matrix such as rock or slag of variable size, shape, and association; these chemical and physical properties may influence the absorption...zirconium, Pb=lead, Cu=copper, Mn=manganese, Si=silicon, Zn= zinc , As=arsenic, Cd=cadmium, CEC= cation exchange capacity, TOC = total organic carbon, Sb

78 FR 13726 - Self-Regulatory Organizations; NYSE Arca, Inc.; Notice of Filing of Amendments No. 1 and No. 2...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-28

... SECURITIES AND EXCHANGE COMMISSION [Release No. 34-68973; File No. SR-NYSEArca-2012-66] Self-Regulatory Organizations; NYSE Arca, Inc.; Notice of Filing of Amendments No. 1 and No. 2 and Order Granting Accelerated Approval of a Proposed Rule Change as Modified by Amendments No. 1 and No. 2 To List and Trade Shares of the iShares Copper Trust...

Comparison between methods using copper, lanthanum, and colorimetry for the determination of the cation exchange capacity of plant cell walls.

PubMed

Wehr, J Bernhard; Blamey, F Pax C; Menzies, Neal W

2010-04-28

The determination of the cation exchange capacity (CEC) of plant cell walls is important for many physiological studies. We describe the determination of cell wall CEC by cation binding, using either copper (Cu) or lanthanum (La) ions, and by colorimetry. Both cations are strongly bound by cell walls, permitting fast and reproducible determinations of the CEC of small samples. However, the dye binding methods using two cationic dyes, Methylene Blue and Toluidine Blue, overestimated the CEC several-fold. Column and centrifugation methods are proposed for CEC determination by Cu or La binding; both provide similar results. The column method involves packing plant material (2-10 mg dry mass) in a chromatography column (10 mL) and percolating with 20 bed volumes of 1 mM La or Cu solution, followed by washing with deionized water. The centrifugation method uses a suspension of plant material (1-2 mL) that is centrifuged, and the pellet is mixed three times with 10 pellet volumes of 1 mM La or Cu solution followed by centrifugation and final washing with deionized water. In both methods the amount of La or Cu bound to the material was determined by spectroscopic methods.

Experimental study of Cu-water nanofluid forced convective flow inside a louvered channel

NASA Astrophysics Data System (ADS)

Khoshvaght-Aliabadi, M.; Hormozi, F.; Zamzamian, A.

2015-03-01

Heat transfer enhancement plays a very important role for energy saving in plate-fin heat exchangers. In the present study, the influences of simultaneous utilization of a louvered plate-fin channel and copper-base deionized water nanofluid on performance of these exchangers are experimentally explored. The effects of flow rate (2-5 l/min) and nanoparticles weight fraction (0-0.4 %) on heat transfer and pressure drop characteristics are determined. Experimental results indicate that the use of louvered channel instead of the plain one can improve the heat transfer performance. Likewise, addition of small amounts of copper nanoparticles to the base fluid augments the convective heat transfer coefficient remarkably. The maximum rise of 21.7 % in the convective heat transfer coefficient is observed for the 0.4 % wt nanofluid compared to the base fluid. Also, pumping power for the base fluid and nanofluids are calculated based on the measured pressure drop in the louvered channel. The average increase in pumping power is 11.8 % for the nanofluid with 0.4 % wt compared to the base fluid. Applied performance criterion shows a maximum performance index of 1.167 for the nanofluid with 0.1 % wt Finally, two correlations are proposed for Nusselt number and friction factor which fit the experimental data with in ±10 %.

Water Based Phase Change Material Heat Exchanger Development

NASA Technical Reports Server (NTRS)

Hansen, Scott W.; Sheth, Ribik B.; Atwell, Matt; Cheek, Ann; Agarwal, Muskan; Hong, Steven; Patel, Aashini,; Nguyen, Lisa; Posada, Luciano

2014-01-01

In a cyclical heat load environment such as low Lunar orbit, a spacecraft’s radiators are not sized to reject the full heat load requirement. Traditionally, a supplemental heat rejection device (SHReD) such as an evaporator or sublimator is used to act as a “topper” to meet the additional heat rejection demands. Utilizing a Phase Change Material (PCM) heat exchanger (HX) as a SHReD provides an attractive alternative to evaporators and sublimators as PCM HXs do not use a consumable, thereby leading to reduced launch mass and volume requirements. Studies conducted in this paper investigate utilizing water’s high latent heat of formation as a PCM, as opposed to traditional waxes, and corresponding complications surrounding freezing water in an enclosed volume. Work highlighted in this study is primarily visual and includes understanding ice formation, freeze front propagation, and the solidification process of water/ice. Various test coupons were constructed of copper to emulate the interstitial pin configuration (to aid in conduction) of the proposed water PCM HX design. Construction of a prototypic HX was also completed in which a flexible bladder material and interstitial pin configurations were tested. Additionally, a microgravity flight was conducted where three copper test articles were frozen continuously during microgravity and 2-g periods and individual water droplets were frozen during microgravity.

Use of Precious Metal-Modifed Nickel-Base Superalloys for Thin Gage Applications (Preprint)

DTIC Science & Technology

2011-04-01

superalloys are being investigated for use in thin gage applications, such as thermal protection systems or heat exchangers, due to their strength and...atomic % total) in place of the platinum and iridium. 15. SUBJECT TERMS thermal protection systems, nickel, superalloy, thermomechanical processing...use in thin gage applications, such as thermal protection systems or heat exchangers, due to their strength and inherent oxidation resistance at

Positive exchange-bias and giant vertical hysteretic shift in La0.3Sr0.7FeO3/SrRuO3 bilayers

PubMed Central

Rana, Rakesh; Pandey, Parul; Singh, R. P.; Rana, D. S.

2014-01-01

The exchange-bias effects in the mosaic epitaxial bilayers of the itinerant ferromagnet (FM) SrRuO3 and the antiferromagnetic (AFM) charge-ordered La0.3Sr0.7FeO3 were investigated. An uncharacteristic low-field positive exchange bias, a cooling-field driven reversal of positive to negative exchange-bias and a layer thickness optimised unusual vertical magnetization shift were all novel facets of exchange bias realized for the first time in magnetic oxides. The successive magnetic training induces a transition from positive to negative exchange bias regime with changes in domain configurations. These observations are well corroborated by the hysteretic loop asymmetries which display the modifications in the AFM spin correlations. These exotic features emphasize the key role of i) mosaic disorder induced subtle interplay of competing AFM-superexchange and FM double exchange at the exchange biased interface and, ii) training induced irrecoverable alterations in the AFM spin structure. PMID:24569516

Efficient replacement of plasma membrane outer leaflet phospholipids and sphingolipids in cells with exogenous lipids

PubMed Central

Kim, JiHyun; Huang, Zhen; St. Clair, Johnna R.; Brown, Deborah A.; London, Erwin

2016-01-01

Our understanding of membranes and membrane lipid function has lagged far behind that of nucleic acids and proteins, largely because it is difficult to manipulate cellular membrane lipid composition. To help solve this problem, we show that methyl-α-cyclodextrin (MαCD)-catalyzed lipid exchange can be used to maximally replace the sphingolipids and phospholipids in the outer leaflet of the plasma membrane of living mammalian cells with exogenous lipids, including unnatural lipids. In addition, lipid exchange experiments revealed that 70–80% of cell sphingomyelin resided in the plasma membrane outer leaflet; the asymmetry of metabolically active cells was similar to that previously defined for erythrocytes, as judged by outer leaflet lipid composition; and plasma membrane outer leaflet phosphatidylcholine had a significantly lower level of unsaturation than phosphatidylcholine in the remainder of the cell. The data also provided a rough estimate for the total cellular lipids residing in the plasma membrane (about half). In addition to such lipidomics applications, the exchange method should have wide potential for investigations of lipid function and modification of cellular behavior by modification of lipids. PMID:27872310

Efficient replacement of plasma membrane outer leaflet phospholipids and sphingolipids in cells with exogenous lipids.

PubMed

Li, Guangtao; Kim, JiHyun; Huang, Zhen; St Clair, Johnna R; Brown, Deborah A; London, Erwin

2016-12-06

Our understanding of membranes and membrane lipid function has lagged far behind that of nucleic acids and proteins, largely because it is difficult to manipulate cellular membrane lipid composition. To help solve this problem, we show that methyl-α-cyclodextrin (MαCD)-catalyzed lipid exchange can be used to maximally replace the sphingolipids and phospholipids in the outer leaflet of the plasma membrane of living mammalian cells with exogenous lipids, including unnatural lipids. In addition, lipid exchange experiments revealed that 70-80% of cell sphingomyelin resided in the plasma membrane outer leaflet; the asymmetry of metabolically active cells was similar to that previously defined for erythrocytes, as judged by outer leaflet lipid composition; and plasma membrane outer leaflet phosphatidylcholine had a significantly lower level of unsaturation than phosphatidylcholine in the remainder of the cell. The data also provided a rough estimate for the total cellular lipids residing in the plasma membrane (about half). In addition to such lipidomics applications, the exchange method should have wide potential for investigations of lipid function and modification of cellular behavior by modification of lipids.

The heat exchanger of small pellet boiler for phytomass

NASA Astrophysics Data System (ADS)

Mičieta, Jozef; Lenhard, Richard; Jandačka, Jozef

2014-08-01

Combustion of pellets from plant biomass (phytomass) causes various troubles. Main problem is slagging ash because of low melting temperature of ash from phytomass. This problem is possible to solve either improving energetic properties of phytomass by additives or modification of boiler construction. A small-scale boiler for phytomass is different in construction of heat exchanger and furnace mainly. We solve major problem - slagging ash, by decreasing combustion temperature via redesign of pellet burner and boiler body. Consequence of lower combustion temperature is also lower temperature gradient of combustion gas. It means that is necessary to design larger heat exchanging surface. We plane to use underfed burner, so we would utilize circle symmetry heat exchanger. Paper deals design of heat exchanger construction with help of CFD simulation. Our purpose is to keep uniform water flux and combustion gas flux in heat exchanger without zone of local overheating and excess cooling.

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

Confer, L.; Kramer, K.L.

A condensing type heat exchanger operating at Henkel Corporation's plant in Kankakee, IL, has enabled the plant to save $400,000 in energy costs within the first 22 months of operation, recouping the initial capital investment for the unit within that time frame. The heat exchanger enables the plant to accomplish what historically was considered taboo - to cool boiler stack gas down to 130/sup 0/F, below the dew point, and thus recover both sensible and latent heat from the gas. Traditionally, moisture could not be squeezed out of stack gas below the recommended temperature of 250/sup 0/F because the stackmore » gas close to the heat exchanger tubes would approach the dew point, condense and attack metal surfaces. The condensing type heat exchanger can withstand corrosive conditions, however, because all wetted surfaces on the flue side of the shell and copper-nickel tube design are protected with an extruded Teflon fluorocarbon resin covering (not coating). The waste heat recovery system was installed over a two-month period in 1985. Performance has been above expectations with greater energy savings than originally projected. The amount of operator attention required is minimal.« less

Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

PubMed

Solomon, Edward I

2016-07-05

Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle.

Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

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

Zheng, Jie; Cullen, David A.; Forest, Robert V.

2015-01-15

The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-raymore » photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.« less

Polyimide surface modification by using microwave plasma for adhesion enhancement of Cu electroless plating.

PubMed

Cho, Sang-Jin; Nguyen, Trieu; Boo, Jin-Hyo

2011-06-01

Microwave (MW) plasma was applied to the surface of polyimide (PI) films as a treatment to enhance the adhesion between copper deposition layer and PI surface for electroless plating. The influences of nitrogen MW plasma treatment on chemical composition of the PI surface were investigated by using X-Ray photoelectron spectroscopy (XPS). The wettability was also investigated by water contact angle measurement. The surface morphologies of PI films before and after treatment were characterized with atomic force microscopy (AFM). The contact angle results show that was dramatically decreased to 16.1 degrees at the optimal treatment condition from 72.1 degrees (untreated PI). However, the root mean square (RMS) roughness of treated PI film was almost unchanged. The AFM roughness was stayed from 1.0 to 1.2 with/without plasma treatment. XPS data show a nitrogen increase when PI films exposed to N2 MW plasma. Electroless copper depositions were carried out with the free-formaldehyde method using glyoxylic acid as the reducing reagent and mixture palladium chloride, tin chloride as activation solution. Adhesion property between polyimide surface and copper layer was investigated by tape test.

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

Sandoval-Paz, M.G., E-mail: myrnasandoval@udec.cl; Rodríguez, C.A.; Porcile-Saavedra, P.F.

Copper (I) selenide thin films with orthorhombic and cubic structure were deposited on glass substrates by using the chemical bath deposition technique. The effects of the solution pH on the films growth and subsequently the structural, optical and electrical properties of the films were studied. Films with orthorhombic structure were obtained from baths wherein both metal complex and hydroxide coexist; while films with cubic structure were obtained from baths where the metal hydroxide there is no present. The structural modifications are accompanied by changes in bandgap energy, morphology and electrical resistivity of the films. - Graphical abstract: “Study of themore » crystallographic phase change on copper (I) selenide thin films prepared through chemical bath deposition by varying the pH of the solution” by M. G. Sandoval-Paz, C. A. Rodríguez, P. F. Porcile-Saavedra, C. Trejo-Cruz. Display Omitted - Highlights: • Copper (I) selenide thin films were obtained by chemical bath deposition. • Orthorhombic to cubic phase change was induced by varying the reaction solution pH. • Orthorhombic phase is obtained mainly from a hydroxides cluster mechanism. • Cubic phase is obtained mainly from an ion by ion mechanism. • Structural, optical and electrical properties are presented as a function of pH.« less

Modification of graphene electronic properties via controllable gas-phase doping with copper chloride

NASA Astrophysics Data System (ADS)

Rybin, Maxim G.; Islamova, Vera R.; Obraztsova, Ekaterina A.; Obraztsova, Elena D.

2018-01-01

Molecular doping is an efficient, non-destructive, and simple method for changing the electronic structure of materials. Here, we present a simple air ambient vapor deposition method for functionalization of pristine graphene with a strong electron acceptor: copper chloride. The doped graphene was characterized by Raman spectroscopy, UV-vis-NIR optical absorption spectroscopy, scanning electron microscopy, and electro-physical measurements performed using the 4-probe method. The effect of charge transfer from graphene to a dopant results in shifting the Fermi level in doped graphene. The change of the electronic structure of doped graphene was confirmed by the tangential Raman peak (G-peak) shift and by the appearance of the gap in the UV-vis-NIR spectrum after doping. Moreover, the charge transfer resulted in a substantial decrease in electrical sheet resistance depending on the doping level. At the highest concentration of copper chloride, a Fermi level shift into the valence band up to 0.64 eV and a decrease in the sheet resistance value by 2.36 times were observed (from 888 Ω/sq to 376 Ω/sq for a single graphene layer with 97% of transparency).

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato

2001-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato; Gula, Michael J.; Xue, Sui; Harvey, James T.

2002-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins.

PubMed

Pesavento, Maria; Sturini, Michela; D'Agostino, Girolamo; Biesuz, Raffaela

2010-02-19

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs-Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition. Copyright 2009. Published by Elsevier B.V.

Standoff detection of hidden objects using backscattered ultra-intense laser-produced x-rays

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

Kuwabara, H.; Mori, Y.; Kitagawa, Y.

2013-08-28

Ultra-intense laser-produced sub-ps X-ray pulses can detect backscattered signals from objects hidden in aluminium containers. Coincident measurements using primary X-rays enable differentiation among acrylic, copper, and lead blocks inside the container. Backscattering reveals the shapes of the objects, while their material composition can be identified from the modification methods of the energy spectra of backscattered X-ray beams. This achievement is an important step toward more effective homeland security.

Modification of a single tryptophan residue in human Cu,Zn-superoxide dismutase by peroxynitrite in the presence of bicarbonate.

PubMed

Yamakura, F; Matsumoto, T; Fujimura, T; Taka, H; Murayama, K; Imai, T; Uchida, K

2001-07-09

Human recombinant Cu,Zn-SOD was reacted with peroxynitrite in a reaction mixture containing 150 mM potassium phosphate buffer (pH 7.4) 25 mM sodium bicarbonate, and 0.1 mM diethylenetriamine pentaacetic acid. Disappearance of fluorescence emission at 350 nm, which could be attributed to modification of a single tryptophan residue, was observed in the modified enzyme with a pH optimum of around 8.4. A fluorescence decrease with the same pH optimum was also observed without sodium bicarbonate, but with less efficiency. Amino acid contents of the modified enzyme showed no significant difference in all amino acids except the loss of a single tryptophan residue of the enzyme. The peroxynitrite-modified enzyme showed an increase in optical absorption around 350 nm and 30% reduced enzyme activity based on the copper contents. The modified enzyme showed the same electron paramagnetic resonance spectrum as that of the control enzyme. The modified Cu,Zn-SOD showed a single protein band in sodium dodecyl sulfate--polyacrylamide gel electrophoresis (SDS--PAGE) and five protein bands in non-denaturing PAGE. From this evidence, we conclude that nitration and/or oxidation of the single tryptophan 32 and partial inactivation of the enzyme activity of Cu,Zn-SOD is caused by a peroxynitrite-carbon dioxide adduct without perturbation of the active site copper integrity.

Curcumin prevents the oxidation and lipid modification of LDL and its inhibition of prostacyclin generation by endothelial cells in culture.

PubMed

Mahfouz, Mohamedain M; Zhou, Sherry Q; Kummerow, Fred A

2009-11-01

Low-density lipoprotein (LDL) was isolated from human plasma and oxidized by 5microM copper sulfate for 4h at 37 degrees C in the absence and presence of 1, 3, 5, 10, or 20microM of curcumin. LDL oxidized in the absence of curcumin (oxLDL) showed an increased levels of conjugated dienes, lipid peroxides (TBARS) and lysolecithin (lysoPC) and a significant loss of polyunsaturated fatty acids (PUFA). LDL oxidized with 5microM copper sulfate in the presence of curcumin caused a significant decrease of conjugated diene, lipid peroxides, lysoPC and significant increase of PUFA compared to oxLDL. These changes were dose dependent and reached a maximum at 5microM curcumin. Incubation of human endothelial cells (EC) with 200microg protein/ml of oxLDL caused a significant decrease of prostacyclin (PGI(2)) generation. LDL oxidized in presence of 5microM curcumin did not show any inhibition of PGI(2) generation compared to the control cells. These results indicate that curcumin is an effective chain-breaking antioxidant which prevents oxidation and lipid modification of LDL. The inhibition of oxLDL on PGI(2) is considered a contributing factor in the pathogenesis of thrombosis and atherosclerosis. Curcumin supplementation could be an effective strategy in preventing LDL oxidation and its impact on atherosclerosis and lesion formation.

Morphology, gas exchange, and chlorophyll content of longleaf pine seedlings in response to rooting volume, copper root pruning, and nitrogen supply in a container nursery

Treesearch

R. Kasten Dumroese; Shi-Jean Susana Sung; Jeremiah R. Pinto; Amy Ross-Davis; D. Andrew Scott

2013-01-01

Few pine species develop a seedling grass stage; this growth phase, characterized by strong, carrot-like taproots and a stem-less nature, poses unique challenges during nursery production. Fertilization levels beyond optimum could result in excessive diameter growth that reduces seedling quality as measured by the root bound index (RBI). We grew longleaf pine (Pinus...

Synthesis of nanoscale copper nitride thin film and modification of the surface under high electronic excitation.

PubMed

Ghosh, S; Tripathi, A; Ganesan, V; Avasthi, D K

2008-05-01

Nanoscale (approximately 90 nm) Copper nitride (Cu3N) films are deposited on borosilicate glass and Si substrates by RF sputtering technique in the reactive environment of nitrogen gas. These films are irradiated with 200 MeV Au15+ ions from Pelletron accelerator in order to modify the surface by high electronic energy deposition of heavy ions. Due to irradiation (i) at incident ion fluence of 1 x 10(12) ions/cm2 enhancement of grains, (ii) at 5 x 10912) ions/cm2 mass transport on the films surface, (iii) at 2 x 10(13) ions/cm2 line-like features on Cu3N/glass and nanometallic structures on Cu3N/Si surface are observed. The surface morphology is examined by atomic force microscope (AFM). All results are explained on the basis of a thermal spike model of ion-solid interaction.

Growth Structure and Properties of Gradient Nanocrystalline Coatings of the Ti-Al-Si-Cu-N System

NASA Astrophysics Data System (ADS)

Ovchinnikov, S. V.; Pinzhin, Yu. P.

2016-10-01

Methods of electron microprobe analysis, X-ray structure analysis and electron microscopy were used to study the element composition and features of the structure-phase, elastic stress state of nanocrystalline coatings of the Ti- Al- Si- Cu- N system with gradient of copper concentration across their thickness. The authors established the effects of element composition modification, non-monotonous behavior of the lattice constant of alloyed nitride and rise in the bending-torsion value of the crystalline lattice in individual nanocrystals to values of around 400 degrees/μm with increase in copper concentration, whereas the sizes of alloyed nitride crystals remained practically unchanged. Mechanical (hardness), adhesion and tribological properties of coatings were examined. Comparative analysis demonstrates higher values of adhesion characteristics in the case of gradient coatings of the Ti- Al- Si- Cu- N system than in the case of single-layer (with constant element concentration) analogues.

Mechanical and spectroscopic properties of metal-containing polyimides

NASA Technical Reports Server (NTRS)

Taylor, L. T.; St.clair, A. K.

1983-01-01

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymerization or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Mechanical and spectroscopic properties of metal containing polyimides

NASA Technical Reports Server (NTRS)

Taylor, L. T.; St. Clair, A. K.

1984-01-01

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymermzation or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Surface Modification of Polyimide for Improving Adhesion Strength by Inductively Coupled Plasma

NASA Astrophysics Data System (ADS)

Byun, Tae Joon; Kim, Sung Il; Kim, Youn Joon; Choi, Yoon Suk; Choi, In Sik; Setsuhara, Yuichi; Geon Han, Jeon

2009-08-01

This study examined the effect of an inductively coupled plasma (ICP) treatment using an argon and helium gas mixture on the adhesion between polyimide and a copper film. Optical emission spectroscopy (OES) of the ICP revealed the emission intensity of helium and argon at various intensities with the helium mixing ratio. The treated polyimide surface was analyzed using a contact angle analyzer, Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The contact angle and RMS roughness ranged from 66 to 31° and 2.3 to 4.1 nm, respectively. XPS showed an increase in C-O bonding. The highest peel strength was 0.43 kgf/cm at a 40% of helium mixing ratio, which contained the highest level of activate species. Overall, an ICP treatment of a polyimide surface with a 40% helium gas mixture improves the adhesion strength between copper and polyimide significantly.

Femtosecond laser induced tunable surface transformations on (111) Si aided by square grids diffraction

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

Han, Weina; Jiang, Lan; Li, Xiaowei, E-mail: lixiaowei@bit.edu.cn

We report an extra freedom to modulate the femtosecond laser energy distribution to control the surface ablated structures through a copper-grid mask. Due to the reduced deposited pulse energy by changing the scanning speed or the pulse fluence, a sequential evolution of three distinctly different surface patterns with periodic distributions is formed, namely, striped ripple lines, ripple microdots, and surface modification. By changing the scanning speed, the number of the multiple dots in a lattice can be modulated. Moreover, by exploring the ablation process through the copper grid mask, it shows an abnormal enhanced ablation effect with strong dependence ofmore » the diffraction-aided fs laser ablated surface structures on polarization direction. The sensitivity shows a quasi-cosinusoid-function with a periodicity of π/2. Particularly, the connection process of striped ripple lines manifests a preferential formation direction with the laser polarization.« less

Synthesis and luminescence properties of iridium(III) azide- and triazole-bisterpyridine complexes.

PubMed

Goldstein, Daniel C; Peterson, Joshua R; Cheng, Yuen Yap; Clady, Raphael G C; Schmidt, Timothy W; Thordarson, Pall

2013-07-26

We describe here the synthesis of azide-functionalised iridium(III) bisterpyridines using the "chemistry on the complex" strategy. The resulting azide-complexes are then used in the copper(I)-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition "click chemistry" reaction to from the corresponding triazole-functionalised iridium(III) bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III) bisterpyridines, but this effect can be reversed by the addition of copper(II) sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III) bisterpyridines can be functionalized for use in "click chemistry" facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

Effects of lime and compost on earthworm (Eisenia fetida) reproduction in copper and arsenic contaminated soils from the Puchuncaví Valley, Chile.

PubMed

Neaman, Alexander; Huerta, Soledad; Sauvé, Sébastien

2012-06-01

The Puchuncaví Valley in central Chile has been exposed to atmospheric depositions from a copper smelter. Nowadays, soils in the surrounding area are acidic and contaminated with Cu and As. The objective of this study was to determine the effectiveness of lime and compost for in situ immobilization of trace elements in the soils of the Puchuncaví Valley by using earthworms as bioindicators of toxicity. The lime and compost treatments significantly increased soil pH and decreased the soluble and exchangeable Zn, exchangeable Cu, and free Cu(2+) activity. However, the compost treatment increased soluble Cu, and soluble and exchangeable As. Lime application had no effect on earthworm reproduction in comparison with the unamended control, whereas the application of compost increased cocoon and juvenile production. There was a spatial variability of soil properties within treatments in the field plots. This allowed the identification of which soil properties were actually having an impact on earthworm reproduction. For both cocoon and juvenile production, soil organic matter (SOM) was a positive factor, i.e., more SOM increased cocoon or juvenile production. The toxicity (negative) factor was total soil As. However, total Cu and total As were well correlated (R(2)=0.80, p<0.001), hence some of the trends could have been masked. In summary, compost treatment was effective in improving the quality of soils of Puchuncaví Valley, increasing earthworm reproduction. Future Chilean legislation on maximum permissible concentrations of trace elements in soils should consider SOM content due to its effect on trace element solubility and bioavailability. Copyright © 2012 Elsevier Inc. All rights reserved.

The application of interference fits for overcoming limitations in clamping methodologies for cryo-cooling first crystal configurations in x-ray monochromators

NASA Astrophysics Data System (ADS)

Stimson, J.; Docker, P.; Ward, M.; Kay, J.; Chapon, L.; Diaz-Moreno, S.

2017-12-01

The work detailed here describes how a novel approach has been applied to overcome the challenging task of cryo-cooling the first monochromator crystals of many of the world’s synchrotrons’ more challenging beam lines. The beam line configuration investigated in this work requires the crystal to diffract 15 Watts of 4-34 keV X-ray wavelength and dissipate the additional 485 watts of redundant X-ray power without significant deformation of the crystal surface. In this case the beam foot print is 25 mm by 25 mm on a crystal surface measuring 38 mm by 25 mm and maintain a radius of curvature of more than 50 km. Currently the crystal is clamped between two copper heat exchangers which have LN2 flowing through them. There are two conditions that must be met simultaneously in this scenario: the crystal needs to be clamped strongly enough to prevent the thermal deformation developing whilst being loose enough not to mechanically deform the diffracting surface. An additional source of error also occurs as the configuration is assembled by hand, leading to human error in the assembly procedure. This new approach explores making the first crystal cylindrical with a sleeve heat exchanger. By manufacturing the copper sleeve to be slightly larger than the silicon crystal at room temperature the sleeve can be slid over the silicon and when cooled will form an interference fit. This has the additional advantage that the crystal and its heat exchanger become a single entity and will always perform the same way each time it is used, eliminating error due to assembly. Various fits have been explored to investigate the associated crystal surface deformations under such a regime

Using ion exchange chromatography to purify a recombinantly expressed protein.

PubMed

Duong-Ly, Krisna C; Gabelli, Sandra B

2014-01-01

Ion exchange chromatography (IEX) separates molecules by their surface charge, a property that can vary vastly between different proteins. There are two types of IEX, cation exhange and anion exchange chromatography. The protocol that follows was designed by the authors for anion exchange chromatography of a recombinantly expressed protein having a pI of 4.9 and containing two cysteine residues and one tryptophan residue, using an FPLC system. Prior to anion exchange, the protein had been salted out using ammonium sulfate precipitation and partially purified via hydrophobic interaction chromatography (see Salting out of proteins using ammonium sulfate precipitation and Use and Application of Hydrophobic Interaction Chromatography for Protein Purification). Slight modifications to this protocol may be made to accommodate both the protein of interest and the availability of equipment. © 2014 Elsevier Inc. All rights reserved.

Patient Protection and Affordable Care Act; exchange and insurance market standards for 2015 and beyond. Final rule.

PubMed

2014-05-27

This final rule addresses various requirements applicable to health insurance issuers, Affordable Insurance Exchanges (``Exchanges''), Navigators, non-Navigator assistance personnel, and other entities under the Patient Protection and Affordable Care Act and the Health Care and Education Reconciliation Act of 2010 (collectively referred to as the Affordable Care Act). Specifically, the rule establishes standards related to product discontinuation and renewal, quality reporting, non-discrimination standards, minimum certification standards and responsibilities of qualified health plan (QHP) issuers, the Small Business Health Options Program, and enforcement remedies in Federally-facilitated Exchanges. It also finalizes: A modification of HHS's allocation of reinsurance collections if those collections do not meet our projections; certain changes to allowable administrative expenses in the risk corridors calculation; modifications to the way we calculate the annual limit on cost sharing so that we round this parameter down to the nearest $50 increment; an approach to index the required contribution used to determine eligibility for an exemption from the shared responsibility payment under section 5000A of the Internal Revenue Code; grounds for imposing civil money penalties on persons who provide false or fraudulent information to the Exchange and on persons who improperly use or disclose information; updated standards for the consumer assistance programs; standards related to the opt-out provisions for self-funded, non-Federal governmental plans and related to the individual market provisions under the Health Insurance Portability and Accountability Act of 1996 including excepted benefits; standards regarding how enrollees may request access to non-formulary drugs under exigent circumstances; amendments to Exchange appeals standards and coverage enrollment and termination standards; and time-limited adjustments to the standards relating to the medical loss ratio (MLR) program. The majority of the provisions in this rule are being finalized as proposed.

Modifying Silicates for Better Dispersion in Nanocomposites

NASA Technical Reports Server (NTRS)

Campbell, Sandi

2005-01-01

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

A review on the application of inorganic nano-structured materials in the modification of textiles: focus on anti-microbial properties.

PubMed

Dastjerdi, Roya; Montazer, Majid

2010-08-01

Textiles can provide a suitable substrate to grow micro-organisms especially at appropriate humidity and temperature in contact to human body. Recently, increasing public concern about hygiene has been driving many investigations for anti-microbial modification of textiles. However, using many anti-microbial agents has been avoided because of their possible harmful or toxic effects. Application of inorganic nano-particles and their nano-composites would be a good alternative. This review paper has focused on the properties and applications of inorganic nano-structured materials with good anti-microbial activity potential for textile modification. The discussed nano-structured anti-microbial agents include TiO(2) nano-particles, metallic and non-metallic TiO(2) nano-composites, titania nanotubes (TNTs), silver nano-particles, silver-based nano-structured materials, gold nano-particles, zinc oxide nano-particles and nano-rods, copper nano-particles, carbon nanotubes (CNTs), nano-clay and its modified forms, gallium, liposomes loaded nano-particles, metallic and inorganic dendrimers nano-composite, nano-capsules and cyclodextrins containing nano-particles. This review is also concerned with the application methods for the modification of textiles using nano-structured materials. Copyright 2010 Elsevier B.V. All rights reserved.

Cooperative oscillations of electron-copper-oxygen interaction: Possible relevance for superconduction theory

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

Tributsch, H.

1989-01-01

Interfaces of copper containing crystallized materials (Cu/sub 5/FeS/sub 4/, CuFeS/sub 2/, Cu/sub 2/S, CuS, CuInS/sub 2/, and CuInSe/sub 2/), exposed to oxidation by H/sub 2/O/sub 2/, undergo sustained electrochemical oscillations. They involve electronic (Cu/sup +/), (Cu/sup 2 +/), and (Cu/sup 3 +/) interactions with chemically bound oxygen similar as in superconducting YBa/sub 2/Cu/sub 3/O/sub 7/ or (La,Sr)/sub 2/CuO/sub 4/ and may be a phenomenon of irreversible thermodynamics which is related to the kind of cooperative electron-copper-oxygen interactions which also give rise to high-temperature superconduction. The relevance of the model system is supported by the formation of the H/sub 2/O/sub 2/more » species on the surface of high-temperature superconducting materials in contact with ambiental humidity. It is shown how, by a simple modification of the interaction mechanism, an oscillatory phenomenon such as that observed with oxidized copper sulfide interfaces, which follows a limiting cycle, can be converted into a triple-state phenomenon. Such a cooperative mechanism that involves a lowest steady state which is unable to turn over energy may be the background for the pairing of electrons or a related cooperative interaction process in superconduction. As a possible support, no interfacial oscillations could yet be induced with Ba/sub 2/Cu/sub 3/Y/sub 7/.« less

Study on dioxygen reduction by mutational modifications of the hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase

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

Morishita, Hirotoshi; Kurita, Daisuke; Kataoka, Kunishige

2014-07-18

Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The singlemore » turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase.« less

Effect of Silver or Copper Nanoparticles-Dispersed Silane Coatings on Biofilm Formation in Cooling Water Systems

PubMed Central

Ogawa, Akiko; Kanematsu, Hideyuki; Sano, Katsuhiko; Sakai, Yoshiyuki; Ishida, Kunimitsu; Beech, Iwona B.; Suzuki, Osamu; Tanaka, Toshihiro

2016-01-01

Biofouling often occurs in cooling water systems, resulting in the reduction of heat exchange efficiency and corrosion of the cooling pipes, which raises the running costs. Therefore, controlling biofouling is very important. To regulate biofouling, we focus on the formation of biofilm, which is the early step of biofouling. In this study, we investigated whether silver or copper nanoparticles-dispersed silane coatings inhibited biofilm formation in cooling systems. We developed a closed laboratory biofilm reactor as a model of a cooling pipe and used seawater as a model for cooling water. Silver or copper nanoparticles-dispersed silane coating (Ag coating and Cu coating) coupons were soaked in seawater, and the seawater was circulated in the laboratory biofilm reactor for several days to create biofilms. Three-dimensional images of the surface showed that sea-island-like structures were formed on silane coatings and low concentration Cu coating, whereas nothing was formed on high concentration Cu coatings and low concentration Ag coating. The sea-island-like structures were analyzed by Raman spectroscopy to estimate the components of the biofilm. We found that both the Cu coating and Ag coating were effective methods to inhibit biofilm formation in cooling pipes. PMID:28773758

A new material for removing heavy metals from water

NASA Technical Reports Server (NTRS)

Philipp, Warren H., Jr.; Street, Kenneth W., Jr.

1994-01-01

The NASA Lewis Research Center developed and is patenting a new high capacity ion exchange material (IEM) that removes toxic metals from contaminated water in laboratory tests. The IEM can be made into many forms, such as thin films, coatings, pellets, and fibers. As a result, it can be adapted to many applications to purify contaminated water wherever it is found, be it in waste water treatment systems, lakes, ponds, industrial plants, or in homes. Laboratory tests have been conducted on aqueous solutions containing only one of the following metal cations: lead, copper, mercury, cadmium, silver, chromium (III), nickel, zinc, and yttrium. Tests were also conducted with: (1) calcium present to determine its effects on the uptake of cadmium and copper, and (2) uranium and lanthanides which are stand-ins for other radioactive elements, (3) drinking water for the removal of copper and lead, and (3) others compositions. The results revealed that the IEM removes all these cations, even in the presence of the calcium. Of particular interest are the results of the tests with the drinking water: the lead concentration was reduced from 142 ppb down to 2.8 ppb (well below the accepted EPA standard).

Aluminum and Other Coatings for the Passivation of Tritium Storage Vessels

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

Spencer, W.; Korinko, P.

Using a highly sensitive residual gas analyzer, the off-gassing of hydrogen, water, and hydrocarbons from surface-treated storage vessels containing deuterium was measured. The experimental storage vessels were compared to a low-off-gassing, electro-polished 304L canister. Alternative vessels were made out of aluminum, or were coatings on 304L steel. Coatings included powder pack aluminide, electro-plated aluminum, powder pack chromide, dense electro-plated chromium, copper plated, and copper plated with 25 and 50 percent nano-diamond. Vessels were loaded with low pressure deuterium to observe exchange with protium or hydrogen as observed with formation of HD and HDO. Off gas of D 2O or possiblemore » CD 4 was observed at mass 20. The main off-gas in all of the studies was H 2. The studies indicated that coatings required significant post-coating treatment to reduce off-gas and enhance the permeation barrier from gases likely added during the coating process. Dense packed aluminum coatings needed heating to drive off water. Electro-plated aluminum, chromium and copper coatings appeared to trap hydrogen from the plating process. Nano-diamond appeared to enhance the exchange rate with hydrogen off gas, and its coating process trapped significant amounts of hydrogen. Aluminum caused more protium exchange than chromium-treated surfaces. Aluminum coatings released more water, but pure aluminum vessels released small amounts of hydrogen, little water, and generally performed well. Chromium coating had residual hydrogen that was difficult to totally outgas but otherwise gave low residuals for water and hydrocarbons. Our studies indicated that simple coating of as received 304L metal will not adequately block hydrogen. The base vessel needs to be carefully out-gassed before applying a coating, and the coating process will likely add additional hydrogen that must be removed. Initial simple bake-out and leak checks up to 350° C for a few hours was found to be inadequate. All of the studies indicated that vessels needed several days of vacuum baking at 350-450° C to fully outgas the residual gases, which were mostly hydrogen. The current standard practice of out-gassing from ultra-clean, electro-polished 304L vessels with both vacuum bake-out and followed by an oxidative bake out to enhance the chromium surface performed the best in these studies.« less

Geochemical speciation and dynamic of copper in tropical semi-arid soils exposed to metal-bearing mine wastes.

PubMed

Perlatti, Fabio; Otero, Xosé Luis; Macias, Felipe; Ferreira, Tiago Osório

2014-12-01

The potentially hazardous effects of rock wastes disposed at open pit in three different areas (Pr: Ore processing; Wr: Waste rock and Bd: Border) of an abandoned copper mine were evaluated in this study, with emphasis on acid drainage generation, metal contamination and copper geochemical dynamics in soils. Samples of waste rock were analyzed by Energy dispersive X-ray fluorescence (XRF), scanning electron microscopy with microanalysis (SEM-EDS) and X-ray diffraction (XRD). Soil samples were analyzed to determine the total metal contents (XRF), mineralogy (XRD), pH (H2O and H2O2), organic and inorganic carbon, % of total N, S and P, particle size, and a sequential extraction procedure was used to identify the different copper fractions. As a result of the prevalence of carbonates over sulphides in the wastes, the soil pH remained close to neutral, with absence of acid mine drainage. The geochemical interaction between these mineral phases seems to be the main mechanism to release Cu(2)(+) ions. Total Cu in soils from the Pr area reached 11,180mg.kg(-1), while in Wr and Bd areas the values reached, on average, 4683 and 1086mg.kg(-1), respectively, indicating a very high level of soil contamination. In the Pr and Wr, the Cu was mainly associated with carbonates and amorphous iron oxides. In the Bd areas, the presence of vegetation has influenced the geochemical behavior of copper by increasing the dissolution of carbonates, affecting the buffer capacity of soils against sulphide oxidation, reducing the pH levels and enhancing the proportion of exchangeable and organic bound Cu. The present findings show that the use of plants or organic amendments in mine sites with high concentration of Cu carbonate-containing wastes should be viewed with caution, as the practice may enhance the mobilization of copper to the environment due to an increase in the rate of carbonates dissolution. Copyright © 2014 Elsevier B.V. All rights reserved.

Copper removal from contaminated soils by soil washing process using camellian-derived saponin

NASA Astrophysics Data System (ADS)

Reyes, Arturo; Fernanda Campos, Maria; Videla, Álvaro; Letelier, María Victoria; Fuentes, Bárbara

2015-04-01

Antofagasta Region in North of Chile has been the main copper producer district in the world. As a consequence of a lack of mining closure regulation, a large number of abandon small-to-medium size metal-contaminated sites have been identified in the last survey performed by the Chilean Government. Therefore, more research development on sustainable reclamation technologies must be made in this extreme arid-dry zone. The objective of this study is to test the effectiveness of soil remediation by washing contaminated soil using camellian-derived saponin for the mobilization of copper. Soil samples were taken from an abandoned copper mine site located at 30 km North Antofagasta city. They were dried and sieved at 75 µm for physico-chemical characterization. A commercial saponin extracted from camellias seed was used as biosurfactant. The soil used contains 67.4 % sand, 26.3 % silt and 6.3 % clay. The soil is highly saline (electric conductivity, 61 mScm-1), with low organic matter content (0.41%), with pH 7.30, and a high copper concentration (2200 mg Kg-1 soil). According to the sequential extraction procedure of the whole soil, copper species are mainly as exchangeable fraction (608.2 mg Kg-1 soil) and reducible fraction (787.3 mg Kg-1 soil), whereas the oxidizable and residual fractions are around 205.7 and 598.8 mg Kg-1 soil, respectively. Soil particles under 75 µm contain higher copper concentrations (1242 mg Kg-1 soil) than the particle fraction over 75 µm (912 mg Kg-1 soil). All washing assays were conducted in triplicate using a standard batch technique with and without pH adjustment. The testing protocols includes evaluation of four solid to liquid ratio (0.5:50; 1.0:50; 2.0:50, and 5.0:50) and three saponin concentrations (0, 1, and 4 mg L-1). After shaking (24 h, 20±1 °C) and subsequently filtration (0.45 µm), the supernatants were analyzed for copper and pH. The removal efficiencies of copper by saponin solutions were calculated in according to the concentrations of copper in aqueous solution and its initial concentration on contaminated soil. It was found along this study that the washing of soils reaches a maximum performance when a 0.5:50 ratio soil:water, and 4 mg L-1 of saponin solution were used, in comparison with any other ratios and saponin dosage evaluated. Moreover, when saponin solution (4 mg L-1) was adjusted at pH 4.0, the efficiency of copper removal increased more than three times (98.3 mg Kg-1 soil) in comparison with the washing without pH adjustment (27.7 mg Kg-1 soil soil). Copper removal was found to be dependent on saponin concentration. The carboxyl group of the saponin hydrophilic head molecule could form copper-aquo complexes, which contribute to the mobilization of copper. However, a low pH is also necessary to solubilize and release copper from soil allowing interaction with saponin. It can be concluded that the use of saponin for washing soils containing copper is a cost-effective and environmental friendly alternative for cleaning and remediation of contaminated soils in the Antofagasta Region.

Hydrogen-Exchange Mass Spectrometry for the Study of Intrinsic Disorder in Proteins

PubMed Central

Balasubramaniam, Deepa; Komives, Elizabeth A.

2012-01-01

Amide hydrogen/deuterium exchange detected by mass spectrometry (HXMS) is seeing wider use for the identification of intrinsically disordered parts of proteins. In this review, we discuss examples of how discovery of intrinsically disordered regions and their removal can aid in structure determination, biopharmaceutical quality control, the characterization of how posttranslational modifications affect weak structuring of disordered regions, the study of coupled folding and binding, and the characterization of amyloid formation. PMID:23099262

Copper desorption from Gelidium algal biomass.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2007-04-01

Desorption of divalent copper from marine algae Gelidium sesquipedale, an algal waste (from agar extraction industry) and a composite material (the algal waste immobilized in polyacrylonitrile) was studied in a batch system. Copper ions were first adsorbed until saturation and then desorbed by HNO(3) and Na(2)EDTA solutions. Elution efficiency using HNO(3) increases as pH decreases. At pH=1, for a solid to liquid ratio S/L=4gl(-1), elution efficiency was 97%, 95% and 88%, the stoichiometric coefficient for the ionic exchange, 0.70+/-0.02, 0.73+/-0.05 and 0.76+/-0.06 and the selectivity coefficient, 0.93+/-0.07, 1.0+/-0.3 and 1.1+/-0.3, respectively, for algae Gelidium, algal waste and composite material. Complexation of copper ions by EDTA occurs in a molar proportion of 1:1 and the elution efficiency increases with EDTA concentration. For concentrations of 1.4, 0.88 and 0.57 mmoll(-1), the elution efficiency for S/L=4gl(-1), was 91%, 86% and 78%, respectively, for algae Gelidium, algal waste and composite material. The S/L ratio, in the range 1-20gl(-1), has little influence on copper recovery by using 0.1M HNO(3). Desorption kinetics was very fast for all biosorbents. Kinetic data using HNO(3) as eluant were well described by the mass transfer model, considering the average metal concentration in the solid phase and the equilibrium relationship given by the mass action law. The homogeneous diffusion coefficient varied between 1.0 x 10(-7)cm(2)s(-1) for algae Gelidium and 3.0 x 10(-7)cm(2)s(-1) for the composite material.

Development of a new passive sampler based on diffusive milligel beads for copper analysis in water.

PubMed

Perez, M; Reynaud, S; Lespes, G; Potin-Gautier, M; Mignard, E; Chéry, P; Schaumlöffel, D; Grassl, B

2015-08-26

A new passive sampler was designed and characterized for the determination of free copper ion (Cu(2+)) concentration in aqueous solution. Each sampling device was composed of a set of about 30 diffusive milligel (DMG) beads. Milligel beads with incorporated cation exchange resin (Chelex) particles were synthetized using an adapted droplet-based millifluidic process. Beads were assumed to be prolate spheroids, with a diameter of 1.6 mm and an anisotropic factor of 1.4. The milligel was controlled in chemical composition of hydrogel (monomer, cross-linker, initiator and Chelex concentration) and characterized in pore size. Two types of sampling devices were developed containing 7.5% and 15% of Chelex, respectively, and 6 nm pore size. The kinetic curves obtained demonstrated the accumulation of copper in the DMG according to the process described in the literature as absorption (and/or adsorption) and release following the Fick's first law of diffusion. For their use in water monitoring, the typical physico-chemical characteristics of the samplers, i.e. the mass-transfer coefficient (k0) and the sampler-water partition coefficient (Ksw), were determined based on a static exposure design. In order to determine the copper concentration in the samplers after their exposure, a method using DMG bead digestion combined to Inductively Coupled Plasma - Atomic Emission Spectrometry (ICP-AES) analysis was developed and optimized. The DMG devices proved to be capable to absorb free copper ions from an aqueous solution, which could be accurately quantified with a mean recovery of 99% and a repeatability of 7% (mean relative uncertainty). Copyright © 2015 Elsevier B.V. All rights reserved.

Development of a novel biochar/PSF mixed matrix membrane and study of key parameters in treatment of copper and lead contaminated water.

PubMed

He, Jinsong; Song, Yihua; Chen, J Paul

2017-11-01

Mixed matrix membrane (MMM) has attracted increasing attentions in various applications, such as water treatment. In this study, an innovative biochar/polysulfone (PSF) mixed matrix hollow fiber membrane was fabricated by incorporating micro-sized biochar particles in the PSF matrix. It was demonstrated that the membrane was more hydrophilic than the pure PSF membrane. Higher water flux was obtained. The adsorption of copper and lead on the MMM increased as the pH was increased with the maximum adsorption capacity observed at pH > 4.5. The adsorption equilibrium was established in 7 and 12 h for lead and copper, respectively. The adsorption kinetics and isotherm followed the intraparticle surface diffusion model and Freundlich isotherm, respectively. The presence of humic acid (HA) had a little effect on the adsorption, while the ionic strength showed an adverse effect on the removal. In addition, the feed concentration and cross flow rate significantly affected the removal efficiency in a continuous filtration mode. The increase in feed concentration and cross flow rate resulted in a reduction in the volume of treated permeate that had the copper/lead concentrations below the regulated levels for drinking water. The MMM exhibited an excellent regeneration-reuse performance in the removal of both copper and lead. Finally, our mechanism studies indicated that the uptake of heavy metals was controlled by a combination of key reactions of complexation, ion-exchange and precipitation. This study indicated that the MMM can be applied as an effective and eco-friendly material for the treatment of heavy metals contaminated water. Copyright © 2017. Published by Elsevier Ltd.

Oligo/Polynucleotide-Based Gene Modification: Strategies and Therapeutic Potential

PubMed Central

Sargent, R. Geoffrey; Kim, Soya

2011-01-01

Oligonucleotide- and polynucleotide-based gene modification strategies were developed as an alternative to transgene-based and classical gene targeting-based gene therapy approaches for treatment of genetic disorders. Unlike the transgene-based strategies, oligo/polynucleotide gene targeting approaches maintain gene integrity and the relationship between the protein coding and gene-specific regulatory sequences. Oligo/polynucleotide-based gene modification also has several advantages over classical vector-based homologous recombination approaches. These include essentially complete homology to the target sequence and the potential to rapidly engineer patient-specific oligo/polynucleotide gene modification reagents. Several oligo/polynucleotide-based approaches have been shown to successfully mediate sequence-specific modification of genomic DNA in mammalian cells. The strategies involve the use of polynucleotide small DNA fragments, triplex-forming oligonucleotides, and single-stranded oligodeoxynucleotides to mediate homologous exchange. The primary focus of this review will be on the mechanistic aspects of the small fragment homologous replacement, triplex-forming oligonucleotide-mediated, and single-stranded oligodeoxynucleotide-mediated gene modification strategies as it relates to their therapeutic potential. PMID:21417933

Structural and theoretical basis for ligand exchange on thiolate monolayer protected gold nanoclusters.

PubMed

Heinecke, Christine L; Ni, Thomas W; Malola, Sami; Mäkinen, Ville; Wong, O Andrea; Häkkinen, Hannu; Ackerson, Christopher J

2012-08-15

Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au(102)(p-MBA)(40)(p-BBT)(4) (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au(102)(p-MBA)(44) as a powerful platform for surface chemical engineering.

Adsorption of aqueous copper on peanut hulls

NASA Astrophysics Data System (ADS)

Davis, Kanika Octavia

A method was established for measuring the adsorption of Cu(II) from aqueous solution to unmodified and modified peanut hulls at constant temperature and pH. Modification of the hulls was performed by oxidation with alkaline hydrogen peroxide. During the modification process, the hydrogen peroxide solubilizes the lignin component, making the surface more porous which increases the availability of binding sites, while simultaneously oxidizing the cellulose. The oxidation of alcohol groups creates more binding sites by creating functional groups such as COO-, which increases chelation to metal ions. Fourier transform infrared spectroscopy confirms delignification of the peanut hulls by the disappearance of carboxyl peaks of the modified hulls, which were originally produced from the lignin content. Although, oxidation is not fully confirmed, it is not ruled out because the expected carboxylate peak (1680 cm-1) maybe overshadowed by a broad peak due to OH bending of water adsorbed to the hulls. Hulls adsorbed copper from solutions in the concentration range of 50-1000 ppm of CuCl2. Concentrations of pre- and post-adsorption solutions were determined using inductively coupled plasma optical emission spectroscopy. The adsorption isotherms were fit to known two and three-parameter models, evaluated and the binding mechanism was inferred. Maximum surface coverage was 3.5 +/- 0.6 mg Cu2+ /g hull for unmodified hulls and 11 +/- 1 mg Cu2+/g hull for modified hulls. The adsorption for the hulls is best described by the Langmuir model, suggesting monolayer, homogeneous adsorption. With a free energy of adsorption of 10.5 +/- 0.9 kJ/mol for unmodified hulls and 14.5 +/-0.4 kJ/mol for modified hulls, the process is categorized as chemisorption for both types of hulls. The adsorption for both hulls is also described by the Redlich-Peterson model, giving beta nearer to 1 than 0, which further suggests homogeneous adsorption described by the Langmuir model. After rinsing the hulls, scanning electron microscopy images coupled with energy dispersive X-ray spectroscopy showed that the percentage of copper on the modified hulls (2.5 %) was greater than on the unmodified hulls (1.6 %). This study concluded that the adsorption of copper using peanut hulls is a potential method for wastewater treatment and delignification and oxidation of the hulls increases the adsorption capacity approximately three-fold.

State-of-the-art survey of joinability of materials for OTEC heat exchangers

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

Beaver, R. J.

1978-12-01

Literature and industrial sources were surveyed to assess, on the basis of apparent economics and reliability, the joinability of both shell-and-tube and compact ocean thermal energy conversion (OTEC) heat exchangers. A no-leak requirement is mandatory to prevent mixing seawater and the ammonia working fluid. The operating temperature range considered is 7 to 28/sup 0/C (45 to 82/sup 0/F). Materials evaluated were aluminum, titanium, copper--nickel, AL-6X austenitic stainless steel, singly and in combination with steel and concrete. Many types of welding and brazing processes, roller expansion, magnaforming, O-ring sealing, and adhesive bonding were considered. The automatic gas tungsten-arc welding process andmore » explosion welding processes are the only two joining processes that now appear to offer the high reliability required of no-leak shell-and-tube heat exchangers. Of these two processes, the gas tungsten-arc welding process appears to be the more economically attractive.« less

Different Evolutionary Modifications as a Guide to Rewire Two-Component Systems

PubMed Central

Krueger, Beate; Friedrich, Torben; Förster, Frank; Bernhardt, Jörg; Gross, Roy; Dandekar, Thomas

2012-01-01

Two-component systems (TCS) are short signalling pathways generally occurring in prokaryotes. They frequently regulate prokaryotic stimulus responses and thus are also of interest for engineering in biotechnology and synthetic biology. The aim of this study is to better understand and describe rewiring of TCS while investigating different evolutionary scenarios. Based on large-scale screens of TCS in different organisms, this study gives detailed data, concrete alignments, and structure analysis on three general modification scenarios, where TCS were rewired for new responses and functions: (i) exchanges in the sequence within single TCS domains, (ii) exchange of whole TCS domains; (iii) addition of new components modulating TCS function. As a result, the replacement of stimulus and promotor cassettes to rewire TCS is well defined exploiting the alignments given here. The diverged TCS examples are non-trivial and the design is challenging. Designed connector proteins may also be useful to modify TCS in selected cases. PMID:22586357

Modification split type air conditioning unit by installing internal heat exchanger and condenser precooling

NASA Astrophysics Data System (ADS)

Ambarita, H.

2018-03-01

In this paper, a modified of air conditioning (AC) system is proposed. In the modified system, an internal heat exchanger and condenser precooling unit are installed. The objective is to explore the effect of the additional equipment to the performance of the system. An AC with compressor power of 1 PK is modified and compared with the original one. The results show that ER of the modified system is higher than the original one in order of 3.6%. The work of the compressor of the modified system is 12.5% lower than work of the compressor without modification. Finally, the COP of the modified system is 11.71% higher than the original one. These facts reveal that the combination of IHX and condenser precooling shows positive impact on the performance of the AC. It is recommended to use the modified system to improve the energy efficiency of the Air Conditioning system.

Instrumentation at the Decade 80 solar house in Tucson, Arizona

NASA Technical Reports Server (NTRS)

1978-01-01

Modifications, problems and solutions for the instrumentation system that occurred during the period from May through September, 1978, are described. The solar house was built to show the use of copper in home building and to demonstrate the use of solar energy to provide space heating and cooling and domestic hot water. The auxiliary energy sources are electrical resistance heating for the domestic hot water and a gas-fired boiler for space heating and operation of the adsorption air conditioning units.

The stability of copper oxo species in zeolite frameworks

DOE PAGES

Vilella, Laia; Studt, Felix

2016-03-07

Cu-exchanged zeolites are promising heterogeneous catalysts, as they provide a confined environment to carry out highly selective reactions. Furthermore, the knowledge of how the zeolite framework and the location of Al atoms therein affect the adsorption of copper species is still not well understood. In this work, DFT was used to investigate the adsorption of potential Cu oxo active species suggested in the literature [Cu(η 2-O 2), Cu(µ-O)Cu, and Cu 2O 2] into zeolites with different pore sizes and shapes (AFI, CHA, TON, MOR, and MFI). The calculations revealed that both monomeric and dimeric Cu oxo species bind strongly tomore » the O atoms of the lattice. For the monometallic species similar adsorption energies are obtained with the different zeolite frameworks, whereas an optimum Al–Al distance is required for the dimeric species.« less

Experimental study and simulation of 63Zn production via proton induce reaction.

PubMed

Rostampour, Malihe; Sadeghi, Mahdi; Aboudzadeh, Mohammadreza; Hamidi, Saeid; Soltani, Naser; Novin, Fatemeh Bolouri; Rahiminejad, Ali; Rajabifar, Saeid

2018-06-01

The 63 Zn was produced by16.8 MeV proton irradiation of natural copper. Thick target yield for 63 Zn in the energy range of 16.8 →12.2 MeV was 2.47 ± 0.12 GBq/μA.h. Reasonable agreement between achieved experimental data and theoretical value of thick target yield for 63 Zn was observed. A simple separation procedure of 63 Zn from copper target was developed using cation exchange chromatography. About 88 ± 5% of the loaded activity was recovered. The performance of FLUKA to reproduce experimental data of thick target yield of 63 Zn is validated. The achieved results from this code were compared with the corresponding experimental data. This comparison demonstrated that FLUKA provides a suitable tool for the simulation of radionuclide production using proton irradiation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Development of 3 and 5kW Fuel Cell Power Plants

DTIC Science & Technology

1985-12-12

automotive type air -cooled (cross-flow) copper heat exchanger (Figure 7.7) was used for water reclamation. A 48V, 0.5A brushless DC blower was used to...and the balance is combusted in ’a burner to supply heat required for the endothermic reforming process. The phosphoric acid fuel cell stack is air ...the use of inter- changeable power conditioners . A microprocessor based con- troller provides event sequencing and system. control during startup

Advanced purification strategy for CueR, a cysteine containing copper(I) and DNA binding protein.

PubMed

Balogh, Ria K; Gyurcsik, Béla; Hunyadi-Gulyás, Éva; Christensen, Hans E M; Jancsó, Attila

2016-07-01

Metal ion regulation is essential for living organisms. In prokaryotes metal ion dependent transcriptional factors, the so-called metalloregulatory proteins play a fundamental role in controlling the concentration of metal ions. These proteins recognize metal ions with an outstanding selectivity. A detailed understanding of their function may be exploited in potential health, environmental and analytical applications. Members of the MerR protein family sense a broad range of mostly late transition and heavy metal ions through their cysteine thiolates. The air sensitivity of latter groups makes the expression and purification of such proteins challenging. Here we describe a method for the purification of the copper-regulatory CueR protein under optimized conditions. In order to avoid protein precipitation and/or eventual aggregation and to get rid of the co-purifying Escherichia coli elongation factor, our procedure consisted of four steps supplemented by DNA digestion. Subsequent anion exchange on Sepharose FF Q 16/10, affinity chromatography on Heparin FF 16/10, second anion exchange on Source 30 Q 16/13 and gel filtration on Superdex 75 26/60 resulted in large amounts of pure CueR protein without any affinity tag. Structure and functionality tests performed with mass spectrometry, circular dichroism spectroscopy and electrophoretic gel mobility shift assays approved the success of the purification procedure. Copyright © 2016 Elsevier Inc. All rights reserved.

Speciation of heavy metals Cu, Ni and Zn by modified BCR sequential extraction procedure in sediments from Banten Bay, Banten Province, Indonesia

NASA Astrophysics Data System (ADS)

Lestari; Budiyanto, F.; Hindarti, D.

2018-02-01

Banten Bay is categorized as a marine area that is busy with marine tourism activities, settlements and also industries. One potential impact of the condition is the occurrence of pollution from both industrial and domestic sources, erosion and sedimentation in the coastal environment. Samples were collected from 25 representative stations in April 2016. Chemical speciation of three heavy metals (Cu, Ni, and Zn) was studied using a modified sequential extraction procedure proposed by the European Standard, Measurements and Testing (SM&T) program, formerly the Community Bureau of Reference (BCR). The aims of this study are to determine geochemical speciation of 4 bounds of metal: acid-soluble, reducible, oxidizable and residual, and to assess their impacts in the sediments of Banten Bay, Indonesia. The result shows that the percentage of Copper (45.90-83.75%), Nickel (18.28-65.66%), and Zinc (30.45-79.51%) were mostly accumulated in residual fraction of the total concentrations. The Risk Assessment Code (RAC) reveals that about 0-7.07% of Copper and 1.11-24.35 % of Zinc at sites exist in exchangeable fraction and therefore, they are in low risk category. While 7.34-34.90 of Ni at sites exists in exchangeable fraction and therefore, it is in medium risk category to aquatic environment.

Chiral ligand-exchange high-performance liquid chromatography with copper (II)-L-phenylalanine complexes for separation of 3,4-dimethoxy-α-methylphenylalanine racemes.

PubMed

Jia, Dong-Xu; Ai, Zheng-Gui; Xue, Ya-Ping; Zheng, Yu-Guo

2014-11-01

L-3, 4-dimethoxy-α-methylphenylalanine (L-DMMD) is an important intermediate for the synthesis of 3-hydroxy-α-methyl-L-tyrosine (L-methyldopa). This paper describes an efficient, accurate, and low-priced method of high-performance liquid chromatography (HPLC) using chiral mobile phase and conventional C18 column to separate L-DMMD from its enantiomers. The effects of ligands, copper salts, organic modifiers, pHs of mobile phase, and temperatures on the retention factors (k') and selectivity (α) were evaluated to achieve optimal separation performance. Then, thermal analysis of the optimal separation conditions was investigated as well. It was confirmed that the optimal mobile phase was composed of 20 % (v/v) methanol, 8 mM L-phenylalanine (L-Phe), and 4 mM cupric sulfate in water of pH 3.2, and the column temperature was set at 20 °C. Baseline separation of two enantiomers could be obtained through the conventional C18 column with a resolution (R) of 3.18 in less than 18 min. Thermodynamic data (∆∆H and ∆∆S) obtained by Van't Hoff plots revealed the chiral separation was an enthalpy-controlled process. To the best of our knowledge, this is the first report regarding the enantioseparation of DMMD by chiral ligand-exchange HPLC.

Oral to nasal tube exchange under fibroscopic view: a new technique for nasal intubation in a predicted difficult airway.

PubMed

Monclus, Enric; Garcés, Antonio; Artés, David; Mabrock, Maged

2008-07-01

For a predicted difficult airway, oral intubation techniques are well established in pediatric anesthesia, but nasotracheal intubation remains a problem. There are many reports concerning this, but the risk of bleeding, added to the lack of cooperation make this procedure difficult and hazardous. We describe a modification of the nasal intubation technique in two stages. First an oral intubation and then exchanging the oral for a nasal tube, in the case of a 13-year-old boy affected by an advanced stage of cherubism. Oral intubation using a laryngeal mask technique has already been reported, but problems appear during the exchange procedure and even more when direct laryngoscopy is impossible. Fiberscopic control of the exchange, and the introduction of a Cook Exchange Catheter into the trachea through the oral tube before withdrawal, permits oxygenation of the patient and acts as a guide for oral tube reintroduction if required.

Novel tag-and-exchange (RMCE) strategies generate master cell clones with predictable and stable transgene expression properties.

PubMed

Qiao, Junhua; Oumard, André; Wegloehner, Wolfgang; Bode, Juergen

2009-07-24

Site-specific recombinases have revolutionized the systematic generation of transgenic cell lines and embryonic stem cells/animals and will ultimately also reveal their potential in the genetic modification of induced pluripotent stem cells. Introduced in 1994, our Flp recombinase-mediated cassette exchange strategy permits the exchange of a target cassette for a cassette with the gene of interest, introduced as a part of an exchange vector. The process is "clean" in the sense that it does not co-introduce prokaryotic vector parts; neither does it leave behind a selection marker. Stringent selection principles provide master cell lines permitting subsequent recombinase-mediated cassette exchange cycles in the absence of a drug selection and with a considerable efficiency (approximately 10%). Exemplified by Chinese hamster ovary cells, the strategy proves to be successful even for cell lines with an unstable genotype.

KSC-95pc586

NASA Image and Video Library

1995-04-17

KENNEDY SPACE CENTER, FLA. - Space Shuttle Main Engine (SSME) No. 2036, the first of the new Block 1 engines to fly, awaits installation into position one of the orbiter Discovery in Orbiter Processing Facility 2 during preparation of the spaceplane for the STS-70 mission. The advanced powerplant features a new high-pressure liquid oxygen turbopump, a two-duct powerhead, a baffleless main injector, a single-coil heat exchanger and start sequence modifications. These modifications are designed to improve both engine performance and safety.

Material Removes Heavy Metal Ions From Water

NASA Technical Reports Server (NTRS)

Philipp, Warren H., Jr.; Street, Kenneth W.; Hill, Carol; Savino, Joseph M.

1995-01-01

New high capacity ion-exchange polymer material removes toxic metal cations from contaminated water. Offers several advantages. High sensitivities for such heavy metals as lead, cadmium, and copper and capable of reducing concentrations in aqueous solutions to parts-per-billion range. Removes cations even when calcium present. Material made into variety of forms, such as thin films, coatings, pellets, and fibers. As result, adapted to many applications to purify contaminated water, usually hard wherever found, whether in wastewater-treatment systems, lakes, ponds, industrial plants, or homes. Another important feature that adsorbed metals easily reclaimed by either destructive or nondestructive process. Other tests show ion-exchange polymer made inexpensively; easy to use; strong, flexible, not easily torn; and chemically stable in storage, in aqueous solutions, and in acidic or basic solution.

Composite anion-exchangers modified with nanoparticles of hydrated oxides of multivalent metals

NASA Astrophysics Data System (ADS)

Maltseva, T. V.; Kolomiets, E. O.; Dzyazko, Yu. S.; Scherbakov, S.

2018-02-01

Organic-inorganic composite ion-exchangers based on anion exchange resins have been obtained. Particles of one-component and two-component modifier were embedded using the approach, which allows us to realize purposeful control of a size of the embedded particles. The approach is based on Ostwald-Freundlich equation, which was adapted to deposition in ion exchange matrix. The equation was obtained experimentally. Hydrated oxides of zirconium and iron were applied to modification, concentration of the reagents were varied. The embedded particles accelerate sorption, the rate of which is fitted by the model equation of chemical reactions of pseudo-second order. When sorption of arsenate ions from very diluted solution (50 µg dm-3) occurs, the composites show higher distribution coefficients comparing with the pristine resin.

Giant perpendicular exchange bias with antiferromagnetic MnN

NASA Astrophysics Data System (ADS)

Zilske, P.; Graulich, D.; Dunz, M.; Meinert, M.

2017-05-01

We investigated an out-of-plane exchange bias system that is based on the antiferromagnet MnN. Polycrystalline, highly textured film stacks of Ta/MnN/CoFeB/MgO/Ta were grown on SiOx by (reactive) magnetron sputtering and studied by x-ray diffraction and Kerr magnetometry. Nontrivial modifications of the exchange bias and the perpendicular magnetic anisotropy were observed as functions of both film thicknesses and field cooling temperatures. In optimized film stacks, a giant perpendicular exchange bias of 3600 Oe and a coercive field of 350 Oe were observed at room temperature. The effective interfacial exchange energy is estimated to be Jeff = 0.24 mJ/m2 and the effective uniaxial anisotropy constant of the antiferromagnet is Keff = 24 kJ/m3. The maximum effective perpendicular anisotropy field of the CoFeB layer is Hani = 3400 Oe. These values are larger than any previously reported values. These results possibly open a route to magnetically stable, exchange biased perpendicularly magnetized spin valves.

Enhancing the Performance of CdSe/CdS Dot-in-Rod Light-Emitting Diodes via Surface Ligand Modification.

PubMed

Rastogi, Prachi; Palazon, Francisco; Prato, Mirko; Di Stasio, Francesco; Krahne, Roman

2018-02-14

The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NC-based optoelectronic devices such as photovoltaic cells, photodetectors, and light-emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide nonradiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligand exchange have been employed to improve the conductance of NC films. However, in LEDs, such surface modifications are more critical because of their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films and investigate their performance in all-solution-processed LEDs. The DiR films maintain high photoluminescence quantum yield, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the photoluminescence. In the LEDs, the ligand exchange boosted the luminance, reaching a fourfold increase from 2200 cd/m 2 for native surfactants to 8500 cd/m 2 for the exchanged aminoethanethiol (AET) ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 to 5.4%. We relate these improvements to the increased conductivity of the emissive layer and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain a deeper insight into the band alignment of the LED structure. The UPS data confirm similar flat-band offsets of the emitting layer to the electron- and hole-transport layers in the case of AET ligands, which translates to more symmetric barriers for charge injection of electrons and holes. Furthermore, the change in solubility of the NCs induced by the ligand exchange allows for a layer-by-layer deposition process of the DiR films, which yields excellent homogeneity and good thickness control and enables the fabrication of all the LED layers (except for cathode and anode) by spin-coating.

Polymers in separation processes

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina; Staszak, Katarzyna

2017-05-01

Application of polymer materials as membranes and ion-exchange resins was presented with a focus on their use for the recovery of metal ions from aqueous solutions. Several membrane techniques were described including reverse osmosis, nanofiltration, ultrafiltration, diffusion and Donnan dialysis, electrodialysis and membrane extraction system (polymer inclusion and supported membranes). Moreover, the examples of using ion-exchange resins in metal recovery were presented. The possibility of modification of the resin was discussed, including hybrid system with metal cation or metal oxide immobilized on polymer matrices or solvent impregnated resin.

Experimental investigation and numerical simulation of a copper micro-channel heat exchanger with HFE-7200 working fluid

NASA Astrophysics Data System (ADS)

Borquist, Eric

Ever increasing cost and consumption of global energy resources has inspired the development of energy harvesting techniques which increase system efficiency, sustainability, and environmental impact by using waste energy otherwise lost to the surroundings. As part of a larger effort to produce a multi-energy source prototype, this study focused on the fabrication and testing of a waste heat recovery micro-channel heat exchanger. Reducing cost and facility requirements were a priority for potential industry and commercial adoption of such energy harvesting devices. During development of the micro-channel heat exchanger, a new fabrication process using mature technologies was created that reduced cost, time, and required equipment. Testing involved filling the micro-channel heat exchanger with 3MTM NovecTM HFE-7200 working fluid. The working fluid was chosen for appropriate physical and environmental properties for the prototypes intended application. Using a dry heat exchanger as the baseline, the addition of the working fluid proved advantageous by increasing energy output by 8% while decreasing overall device temperatures. Upon successful experimental testing of the physical device, internal operation was determined based on implementation of the lattice Boltzmann method, a physics-based statistical method that actively tracked the phase change occurring in a simulated micro-channel. The simulation demonstrated three primary areas of phase change occurring, surfaces adjacent to where the heat source and heat sink were located and the bulk vapor-liquid interface, which agreed with initial device design intentions. Condensation film thickness grew to 5microm over the time interval, while the bulk interface tracked from initial 12microm from the lid to 20microm from the lid. Surface tension effects dominating vapor pressure kept the liquid near the heat source; however, the temperature and pressure VLE data suggested vapor interface growth from the heated surface to 5microm above the heated copper plate. Reinforcing the simulation results, including location and movement of phase interfaces, was accomplished through a thorough ten dimensionless number analyses. These specialized ratios indicated dominant fluid and heat transfer behavior including phase change conditions. Thus, fabrication and empirical results for the heat energy harvesting prototype were successful and computational modeling provided understanding of applicable internal system behavior.

PTFE-nanocomposites structure and wear-resistance changing in various methods of structural modification

NASA Astrophysics Data System (ADS)

Mashkov, Yu K.; Ruban, A. S.; Rogachev, E. A.; Chemisenko, O. V.

2018-01-01

Conditions of polymer materials usage containing nanoelements as modifiers significantly affect the requirements for their physic-mechanical and tribological properties. However, the mechanisms of nanoparticles effect to the polymers tribotechnical properties have not been studied enough. The article aim is to analyze the results of studying polytetrafluoroethylene modified with cryptocrystalline graphite and silicon dioxide and to determine the effectiveness of the modification methods used and methods for further improving filled PTFE mechanical and tribotechnical properties. The effect of modifiers to PCM supramolecular structure was analyzed with SEM methods. The results of modifying the PCM samples surface by depositing a copper film with ion-vacuum deposition methods and changing the structural-phase composition and tribological characteristics are considered. The findings make possible to characterize the physicochemical processes under frictional interaction in metal polymer tribosystems.

Evaluation of exchange-correlation functionals for time-dependent density functional theory calculations on metal complexes.

PubMed

Holland, Jason P; Green, Jennifer C

2010-04-15

The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) < 3.5% and epsilon(SF) values close to unity (>0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes. 2009 Wiley Periodicals, Inc.

Performance of a Thermoelectric Device with Integrated Heat Exchangers

NASA Astrophysics Data System (ADS)

Barry, Matthew M.; Agbim, Kenechi A.; Chyu, Minking K.

2015-06-01

Thermoelectric devices (TEDs) convert heat directly into electrical energy, making them well suited for waste heat recovery applications. An integrated thermoelectric device (iTED) is a restructured TED that allows more heat to enter the p-n junctions, thus producing a greater power output . An iTED has heat exchangers incorporated into the hot-side interconnectors with flow channels directing the working fluid through the heat exchangers. The iTED was constructed of p- and n-type bismuth-telluride semiconductors and copper interconnectors and rectangular heat exchangers. The performance of the iTED in terms of , produced voltage and current , heat input and conversion efficiency for various flow rates (), inlet temperatures (C) ) and load resistances () with a constant cold-side temperature ( = 0C) was conducted experimentally. An increase in had a greater effect on the performance than did an increase in . A 3-fold increase in resulted in a 3.2-, 3.1-, 9.7-, 3.5- and 2.8-fold increase in and respectively. For a constant of 50C, a 3-fold increase in from 3300 to 9920 resulted in 1.6-, 1.6-, 2.6-, 1.5- and 1.9-fold increases in , , , and respectively.

Fabrication and testing of microchannel heat exchangers

NASA Astrophysics Data System (ADS)

Cuta, Judith M.; Bennett, Wendy D.; McDonald, Carolyn E.; Ravigururajan, T. S.

1995-09-01

Micro-channel heat-exchanger test articles were fabricated and performance tested. The heat exchangers are being developed for innovative applications, and have been shown to be capable of handling heat loads of up to 100 W/cm2. The test articles were fabricated to represent two different designs for the micro-channel portion of the heat exchanger. One design consists of 166 micro-channels etched in silicon substrate, and a second design consists of 54 micro-channels machined in copper substrate. The devices were tested in an experimental loop designed for performance testing in single- and two-phase flow with water and R124. Pressure and liquid subcooling can be regulated over the range of interest, and a secondary heat removal loop provides stable loop performance for steady-state tests. The selected operating pressures are approximately 0.344 MPa for distilled water and 0.689 MPa for R124. The temperature ranges are 15.5 to 138 C for distilled water and 15.5 to 46 C for R-124. The mass flow range 7.6 X 10-8 to 7.6 X 10MIN5 kg/min for both distilled water and R124.

Tuning the Magnetic Properties of Metal Oxide Nanocrystal Heterostructures by Cation Exchange

PubMed Central

2013-01-01

For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal’s magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe2+ to Co2+ cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co2+ is demonstrated. By applying the cation exchange to FeO/CoFe2O4 core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system. PMID:23362940

The structure and inhibition of human diamine oxidase†,‡

PubMed Central

McGrath, Aaron P; Hilmer, Kimberly M; Collyer, Charles A; Shepard, Eric M; Elmore, Bradley O.; Brown, Doreen E; Dooley, David M; Guss, J Mitchell

2009-01-01

Humans have three functioning genes that code for copper-containing amine oxidases. The product of the AOC1 gene is a so-called diamine oxidase (hDAO), named for its substrate preference for diamines, particularly histamine. hDAO has been cloned and expressed in insect cells and the structure of the native enzyme determined by X-ray crystallography to a resolution of 1.8 Å. The homodimeric structure has the archetypal amine oxidase fold. Two active sites, one in each subunit, are characterized by the presence of a copper ion and a topaquinone residue formed by the post-translational modification of a tyrosine. Although hDAO shares 37.9 % sequence identity with another human copper amine oxidase, semicarbazide sensitive amine oxidase or vascular adhesion protein-1, its substrate binding pocket and entry channel are distinctly different in accord with the different substrate specificities. The structures of two inhibitor complexes of hDAO, berenil and pentamidine, have been refined to resolutions of 2.1 Å and 2.2 Å, respectively. They bind non-covalently in the active site channel. The inhibitor binding suggests that an aspartic acid residue, conserved in all diamine oxidases but absent from other amine oxidases, is responsible for the diamine specificity by interacting with the second amino group of preferred diamine substrates. PMID:19764817

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

PubMed Central

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

2017-01-01

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

Copper and nitrophenol pollutants removal by Na-montmorillonite/alginate microcapsules.

PubMed

Ely, Abdellahi; Baudu, Michel; Basly, Jean-Philippe; Kankou, Mohamed Ould Sid'Ahmed Ould

2009-11-15

The use of renewable bioresources allows the development of low cost adsorbents that are versatile. In the present paper, the affinity and the removal capacity of montmorillonite/alginate microcapsules for a hydrophobic organic pollutant (4-nitrophenol) and an inorganic pollutant (copper) were evaluated. The physicochemical processes through sorption and kinetic experiments under different ratios of montmorillonite vs. alginate and initial contaminant concentrations were investigated. The total weight loss and diameter decrease during the drying process were 90-96% and 64%, respectively. A significant decrease in beads diameter, related to water elimination, has been observed during the first 24h. Structural modifications that occur during the drying process were evaluated using thermal analysis. From correlation coefficients, the second-order equation depicts properly the adsorption of copper by the microbeads adsorption capacity increases to saturation with time; 3 and 6h were needed to reach equilibrium on wet and dry mixed microcapsules. The pseudo-second order model properly depicts the adsorption process of 4-NP onto Na-mont and (Na-mont/SA) mixed microcapsules but failed to reproduce the data observed for the alginate beads. Isotherms data were fitted with good correlation using the Langmuir model; alginate and montmorillonite adsorption capacities (q(m)/wet beads) agree with those obtained by various studies.

Optimization of staged bioleaching of low-grade chalcopyrite ore in the presence and absence of chloride in the irrigating lixiviant: ANFIS simulation.

PubMed

Vakylabad, Ali Behrad; Schaffie, Mahin; Naseri, Ali; Ranjbar, Mohammad; Manafi, Zahra

2016-07-01

In this investigation, copper was bioleached from a low-grade chalcopyrite ore using a chloride-containing lixiviant. In this regard, firstly, the composition of the bacterial culture media was designed to control the cost in commercial application. The bacterial culture used in this process was acclimated to the presence of chloride in the lixiviant. Practically speaking, the modified culture helped the bio-heap-leaching system operate in the chloridic media. Compared to the copper recovery from the low-grade chalcopyrite by bioleaching in the absence of chloride, bioleaching in the presence of chloride resulted in improved copper recovery. The composition of the lixiviant used in this study was a modification with respect to the basal salts in 9 K medium to optimize the leaching process. When leaching the ore in columns, 76.81 % Cu (based on solid residues of bioleaching operation) was recovered by staged leaching with lixiviant containing 34.22 mM NaCl. The quantitative findings were supported by SEM/EDS observations, X-ray elemental mapping, and mineralogical analysis of the ore before and after leaching. Finally, Adaptive neuro-fuzzy inference system (ANFIS) was used to simulate the operational parameters affecting the bioleaching operation in chloride-sulfate system.

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

PubMed

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

2017-08-09

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

Grafting polycaprolactone diol onto cellulose nanocrystals via click chemistry: Enhancing thermal stability and hydrophobic property.

PubMed

Zhou, Ling; He, Hui; Li, Mei-Chun; Huang, Siwei; Mei, Changtong; Wu, Qinglin

2018-06-01

Hydrophobic and thermally-stable cellulose nanocrystals (CNCs) were synthesized by polycarpolactone diol (PCL diol) grafting via click chemistry strategy. The synthesis was designed as a three-step procedure containing azide-modification of CNCs, alkyne-modification of PCL diol and sequent copper(I)-catalyzed azide-alkyne cycloaddition reaction. The structure of azide-modified CNCs and alkyne-modified PCL diol, the structure, hydrophobic ability and thermal stability of click products CNC-PCL were characterized. FTIR, XPS and H 1 NMR results indicated a successful grafting of the N 3 groups onto the CNCs, synthesis of PCL diol-CCH, and formation of the CNC-PCL material. CNC-PCL had enhanced dispersion in the non-polar solvent chloroform owing to the well-maintained microscale size and PCL-induced hydrophobic surface. The thermal stability of CNC-PCL was largely increased due to the grafting of thermally-stable PCL. This work demonstrates that click chemistry is an attractive modification strategy to graft CNCs with polyester chains for further potential application in polymer composites. Copyright © 2018 Elsevier Ltd. All rights reserved.

High temperature sorbents for oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor)

1994-01-01

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C comprising a porous alumina silicate support, such as zeolite, containing from 1 to 10 percent by weight of ion exchanged transition metal, such as copper or cobalt ions, and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum is described. The activation temperature, oxygen sorption, and reducibility are all improved by the presence of the platinum activator.

Transformations of Heavy Metals and Plant Nutrients in Dredged Sediments as Affected by Oxidation Reduction Potential and pH. Volume 1. Literature Review

DTIC Science & Technology

1977-05-01

895-896 (1974). 191. Fagerstrom, T., and Jernelov, A. "Formation of Methyl Mercury from Pure Mercuric Sulphide in Aerobic Organic Sediment." Water...was available. The toxic and nutrient elements included are lead, cadmium, mercury , arsenic, selenium, copper, zinc, manganese, iron, nitrogen...on the exchange of these materials between sediment and water. The toxic and nutrient elements included are lead, cadmium, mercury , ar- senic

A laboratory exercise using a physical model for demonstrating countercurrent heat exchange.

PubMed

Loudon, Catherine; Davis-Berg, Elizabeth C; Botz, Jason T

2012-03-01

A physical model was used in a laboratory exercise to teach students about countercurrent exchange mechanisms. Countercurrent exchange is the transport of heat or chemicals between fluids moving in opposite directions separated by a permeable barrier (such as blood within adjacent blood vessels flowing in opposite directions). Greater exchange of heat or chemicals between the fluids occurs when the flows are in opposite directions (countercurrent) than in the same direction (concurrent). When a vessel loops back on itself, countercurrent exchange can occur between the two arms of the loop, minimizing loss or uptake at the bend of the loop. Comprehension of the physical principles underlying countercurrent exchange helps students to understand how kidneys work and how modifications of a circulatory system can influence the movement of heat or chemicals to promote or minimize exchange and reinforces the concept that heat and chemicals move down their temperature or concentration gradients, respectively. One example of a well-documented countercurrent exchanger is the close arrangement of veins and arteries inside bird legs; therefore, the setup was arranged to mimic blood vessels inside a bird leg, using water flowing inside tubing as a physical proxy for blood flow within blood vessels.

On-tissue Direct Monitoring of Global Hydrogen/Deuterium Exchange by MALDI Mass Spectrometry: Tissue Deuterium Exchange Mass Spectrometry (TDXMS)*

PubMed Central

Quanico, Jusal; Franck, Julien

2016-01-01

Hydrogen/deuterium exchange mass spectrometric (H/DXMS) methods for protein structural analysis are conventionally performed in solution. We present Tissue Deuterium Exchange Mass Spectrometry (TDXMS), a method to directly monitor deuterium uptake on tissue, as a means to better approximate the deuterium exchange behavior of proteins in their native microenvironment. Using this method, a difference in deuterium uptake behavior was observed when the same proteins were monitored in solution and on tissue. The higher maximum deuterium uptake at equilibrium for all proteins analyzed in solution suggests a more open conformation in the absence of interacting partners normally observed on tissue. We also demonstrate a difference in the deuterium uptake behavior of a few proteins across different morphological regions of the same tissue section. Modifications of the total number of hydrogens exchanged, as well as the kinetics of exchange, were both observed. These results provide information on the implication of protein interactions with partners as well as on the conformational changes related to these interactions, and illustrate the importance of examining protein deuterium exchange behavior in the presence of its specific microenvironment directly at the level of tissues. PMID:27512083

Modification of the quality of water injected into Louisiana gulf coast sands: Effects of cation exchange

NASA Astrophysics Data System (ADS)

Hanor, Jeffrey S.

1982-06-01

Interest in artificially recharging selected shallow sands in South Louisiana with fresh water has been stimulated by the desire to retard contamination of municipal groundwater supplies by brackish water, to retard ground subsidence and decrease pumping lifts, and to develop emergency subsurface supplies of potable water for communities dependent on surface waters susceptible to contamination. Results of field experiments, laboratory work, and model calculations demonstrate that ion exchange reactions involving clays dispersed in aquifer sands can be expected to modify significantly the composition of waters injected into Gulf Coast sediments. As little as 0.1 weight percent smectite (montmorillonite) can remove, by exchange with absorbed Na, a significant fraction of the dissolved Ca and Mg present in the injected water. The hardness of the water is thus reduced, which may be a desirable modification in water quality. Exchange occurs as fast as the fluids can be pumped into or out of the aquifer, and the water-softening capacity of the aquifer can be restored by allowing sodium-rich native pore waters to sweep back over the dispersed clays. Each acre of an aquifer 50 feet thick and containing 0.1 wt % smectite could soften half a million gallons of injected Mississippi River water. Many individual Gulf Coast aquifers underlie tens of thousands of acres, and their potential softening capacity is thus enormous. Additional exchange processes involving adjacent aquitard shales presumably will operate over long-term periods. It is possible that Gulf Coast aquifers will be used at some point in the future as processing plants to treat injected water to improve its quality for a variety of municipal and industrial purposes.

Application of the exact exchange potential method for half metallic intermediate band alloy semiconductor.

PubMed

Fernández, J J; Tablero, C; Wahnón, P

2004-06-08

In this paper we present an analysis of the convergence of the band structure properties, particularly the influence on the modification of the bandgap and bandwidth values in half metallic compounds by the use of the exact exchange formalism. This formalism for general solids has been implemented using a localized basis set of numerical functions to represent the exchange density. The implementation has been carried out using a code which uses a linear combination of confined numerical pseudoatomic functions to represent the Kohn-Sham orbitals. The application of this exact exchange scheme to a half-metallic semiconductor compound, in particular to Ga(4)P(3)Ti, a promising material in the field of high efficiency solar cells, confirms the existence of the isolated intermediate band in this compound. (c) 2004 American Institute of Physics.

Mass spectrometry-based carboxyl footprinting of proteins: Method evaluation

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

Zhang, Hao; Wen, Jianzhong; Huang, Richard Y-C.

2012-02-01

Protein structure determines function in biology, and a variety of approaches have been employed to obtain structural information about proteins. Mass spectrometry-based protein footprinting is one fast-growing approach. One labeling-based footprinting approach is the use of a water-soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and glycine ethyl ester (GEE) to modify solvent-accessible carboxyl groups on glutamate (E) and aspartate (D). This paper describes method development of carboxyl-group modification in protein footprinting. The modification protocol was evaluated by using the protein calmodulin as a model. Because carboxyl-group modification is a slow reaction relative to protein folding and unfolding, there is an issue that modificationsmore » at certain sites may induce protein unfolding and lead to additional modification at sites that are not solvent-accessible in the wild-type protein. We investigated this possibility by using hydrogen deuterium amide exchange (H/DX). The study demonstrated that application of carboxyl group modification in probing conformational changes in calmodulin induced by Ca{sup 2+} binding provides useful information that is not compromised by modification-induced protein unfolding.« less

Copper-transporting P-type ATPases use a unique ion-release pathway

PubMed Central

Andersson, Magnus; Mattle, Daniel; Sitsel, Oleg; Nielsen, Anna Marie; White, Stephen H.; Nissen, Poul; Gourdon, Pontus

2014-01-01

Heavy metals in cells are typically regulated by PIB-type ATPases such as the copper transporting Cu+-ATPases. The first crystal structure of a Cu+-ATPase (LpCopA) was trapped in a transition state of dephosphorylation (E2.Pi) and inferred to be occluded. The structure revealed a PIB-specific topology and suggested a copper transport pathway across the membrane. Here we show by molecular dynamics (MD) simulations that extracellular water solvates the transmembrane (TM) domain, indicative of a pathway for Cu+ release. Furthermore, a new LpCopA crystal structure determined at 2.8 Å resolution, trapped in the E2P state (which is associated with extracellular exchange in PII-type ATPases), delineates the same conduit as also further supported by site-directed mutagenesis. The E2P and E2.Pi states therefore appear equivalent and open to the extracellular side, in contrast to PII-type ATPases where the E2.Pi state is occluded. This indicates that Cu+-ATPases couple dephosphorylation differently to the conformational changes associated with ion extrusion. The ion pathway may explain why Menkes’ and Wilson’s disease mutations at the extracellular side impair protein function, and points to an accessible site for novel inhibitors targeting Cu+-ATPases of pathogens. PMID:24317491

Role of the constant region domain in the structural diversity of human antibody light chains.

PubMed

Hifumi, Emi; Taguchi, Hiroaki; Kato, Ryuichi; Uda, Taizo

2017-04-01

Issues regarding the structural diversity (heterogeneity) of an antibody molecule have been the subject of discussion along with the development of antibody drugs. Research on heterogeneity has been extensive in recent years, but no clear solution has been reached. Heterogeneity is also observed in catalytic antibody κ light chains (CLs). In this study, we investigated how the constant region domain of CLs concerns structural diversity because it is a simple and good example for elucidating heterogeneity. By means of cation-exchange chromatography, SDS-PAGE, and 2-dimensional electrophoresis for the CL, multimolecular forms consisting of different electrical charges and molecular sizes coexisted in the solution, resulting in the similar heterogeneity of the full length of CLs. The addition of copper ion could cause the multimolecular forms to change to monomolecular forms. Copper ion contributed greatly to the enrichment of the dimer form of CL and the homogenization of the differently charged CLs. Two molecules of the CL protein bound one copper ion. The binding affinity of the ion was 48.0 μM -1 Several divalent metal ions were examined, but only zinc showed a similar effect.-Hifumi, E., Taguchi, H., Kato, R., Uda, T. Role of the constant region domain in the structural diversity of human antibody light chains. © FASEB.

Adsorption characteristics of Copper (Ⅱ), Zinc (Ⅱ) and Mercury (Ⅱ) by four kinds of immobilized fungi residues.

PubMed

Li, Xia; Zhang, Dan; Sheng, Fei; Qing, Hui

2018-01-01

This study investigated the adsorption characteristics of Copper (Ⅱ), Zinc (Ⅱ) and Mercury (Ⅱ) by immobilized Flammulina velutipes, Auricularia polytricha, Pleurotus eryngii and Pleurotus ostreatus residues. Lagergren model, elovich and intraparticle diffusion model were used to present the adsorption kinetics, and it was proved that Langmuir isotherm model and pseudo-second order kinetics are the best suitable model with high correlation coefficient to characterize the adsorption process of Copper (Ⅱ), Zinc (Ⅱ) and Mercury (Ⅱ). The results showed that adsorption process finished in 120min at pH 6.0. The adsorption rate of Cu 2+ , Zn 2+ and Hg 2+ were reached to 53.8-84.1% of total in the initial 60min, and finished in 120min. Ion exchange and complexation of F. velutipes were the main mechanisms for adsorption of metal ions by characterizations of Scanning electron microscopy (SEM) and Fourier transform infrared (FTIR). In addition the functional group of cell walls such as hydroxyl, amide, carbonyl, phosphoric played a critical role in ions adsorption of edible mushroom residues. Cu 2+ , Zn 2+ and Hg 2+ in wastewater could be efficiently removed by F. velutipes residue with removal ratio of 73.11%, 66.67% and 69.35%, respectively. Copyright © 2017 Elsevier Inc. All rights reserved.

Biosorption of copper by marine algae Gelidium and algal composite material in a packed bed column.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Loureiro, José M; Boaventura, Rui A R

2008-09-01

Marine algae Gelidium and algal composite material were investigated for the continuous removal of Cu(II) from aqueous solution in a packed bed column. The biosorption behaviour was studied during one sorption-desorption cycle of Cu(II) in the flow through column fed with 50 and 25 mg l(-1) of Cu(II) in aqueous solution, at pH 5.3, leading to a maximum uptake capacity of approximately 13 and 3 mg g(-1), respectively, for algae Gelidium and composite material. The breakthrough time decreases as the inlet copper concentration increases, for the same flow rate. The pH of the effluent decreases over the breakthrough time of copper ions, which indicates that ion exchange is one of the mechanisms involved in the biosorption process. Temperature has little influence on the metal uptake capacity and the increase of the ionic strength reduces the sorption capacity, decreasing the breakthrough time. Desorption using 0.1M HNO(3) solution was 100% effective. After two consecutive sorption-desorption cycles no changes in the uptake capacity of the composite material were observed. A mass transfer model including film and intraparticle resistances, and the equilibrium relationship, for adsorption and desorption, was successfully applied for the simulation of the biosorption column performance.

Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination

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

Mossine, Andrew V.; Brooks, Allen F.; Ichiishi, Naoko

In a relatively short period of time, transition metal-mediated radiofluorination reactions have changed the PET radiochemistry landscape. These reactions have enabled the radiofluorination of a wide range of substrates, facilitating access to radiopharmaceuticals that were challenging to synthesize using traditional fluorine-18 radiochemistry. However, the process of adapting these new reactions for automated radiopharmaceutical production has revealed limitations in fitting them into the confines of traditional radiochemistry systems. In particular, the presence of bases (e.g. K 2CO 3) and/or phase transfer catalysts (PTC) (e.g. kryptofix 2.2.2) associated with fluorine-18 preparation has been found to be detrimental to reaction yields. We hypothesizedmore » that these limitations could be addressed through the development of alternate techniques for preparing [18F]fluoride. This approach also opens the possibility that an eluent can be individually tailored to meet the specific needs of a metal-catalyzed reaction of interest. In this communication, we demonstrate that various solutions of copper salts, bases, and ancillary ligands can be utilized to elute [ 18F]fluoride from ion exchange cartridges. The new procedures we present here are effective for fluorine-18 radiochemistry and, as proof of concept, have been used to optimize an otherwise base-sensitive copper-mediated radiofluorination reaction.« less

Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination

DOE PAGES

Mossine, Andrew V.; Brooks, Allen F.; Ichiishi, Naoko; ...

2017-03-22

In a relatively short period of time, transition metal-mediated radiofluorination reactions have changed the PET radiochemistry landscape. These reactions have enabled the radiofluorination of a wide range of substrates, facilitating access to radiopharmaceuticals that were challenging to synthesize using traditional fluorine-18 radiochemistry. However, the process of adapting these new reactions for automated radiopharmaceutical production has revealed limitations in fitting them into the confines of traditional radiochemistry systems. In particular, the presence of bases (e.g. K 2CO 3) and/or phase transfer catalysts (PTC) (e.g. kryptofix 2.2.2) associated with fluorine-18 preparation has been found to be detrimental to reaction yields. We hypothesizedmore » that these limitations could be addressed through the development of alternate techniques for preparing [18F]fluoride. This approach also opens the possibility that an eluent can be individually tailored to meet the specific needs of a metal-catalyzed reaction of interest. In this communication, we demonstrate that various solutions of copper salts, bases, and ancillary ligands can be utilized to elute [ 18F]fluoride from ion exchange cartridges. The new procedures we present here are effective for fluorine-18 radiochemistry and, as proof of concept, have been used to optimize an otherwise base-sensitive copper-mediated radiofluorination reaction.« less

76 FR 2705 - Notice of Realty Action; Modification of the Segregative Effect of Recreation and Public Purposes...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-14

... action will modify the segregation to open the lands only to effect this exchange. FOR FURTHER... lease on November 3, 1978, and published in the Federal Register (62 FR 9446) which included segregation...

Low-temperature Raman spectroscopy of copper and silver nanoparticles ion-synthesized in a silica glass and subjected to laser annealing

NASA Astrophysics Data System (ADS)

Kurbatova, N. V.; Galyautdinov, M. F.; Shtyrkov, E. I.; Nuzhdin, V. I.; Stepanov, A. L.

2010-06-01

The modification of the shape of ion-synthesized silver and copper nanoparticles in a silica glass during laser annealing has been studied for the first time by Raman spectroscopy at a temperature of 77 K. The laser annealing has been carried out for a wavelength of 694 nm at the edge of the plasmon absorption spectrum of nanoparticles. A comparison of the experimental spectra and the calculated modes of in-phase bending vibrations of the “harmonica” type in nanostrings of the corresponding metals has demonstrated their good agreement. The effects observed have been discussed from the standpoint of the size quantization of vibrations in metal nanowires. This methodical approach has made it possible to estimate the sizes of the Ag and Cu nanoparticles under the assumption that they have an elongated form; in this case, their average lengths are equal to 2.5 and 1.4 nm, respectively.

Copper sulfide nanodisk as photoacoustic contrast agent for ovarian tumor detection

NASA Astrophysics Data System (ADS)

Wang, Junxin; Hsu, Su-Wen; Tao, Andrea R.; Jokerst, Jesse V.

2017-03-01

Ultrasound is broadly used in the clinics yet is limited in early cancer detection because of its poor contrast between healthy and diseased tissues. Photoacoustic imaging can improve this limitation and has been extensively studied in pre-clinical models. Contrast agents can help improve the accuracy of diagnosis. We recently reported a novel copper sulfide (CuS) nanodisk with strong directionally-localized surface plasmon resonance in the near infrared region. This plasmonic resonance of nanodisks is tunable by changing the size and aspect ratio of CuS nanodisk. Here, we demonstrate this CuS nanodisk is a strong photoacoustic contrast agent. We prepared CuS nanodisks via a solvent-based synthesis followed by surface modification of poly(ethylene glycol) methyl ether thiol for in vivo applications. These CuS nanodisks can be detected at a concentration as low as 26 pM at 920 nm. Their nanosize and strong photoacoustic response make this novel CuS nanodisk a strong candidate for photoacoustic cancer imaging.

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.

Anomalous expansion of the copper-apical-oxygen distance in superconducting cuprate bilayers

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

Zhou, Hua; Yacoby, Yizhak; Butko, Vladimir Y.

2010-08-27

We have introduced an improved x-ray phase-retrieval method with unprecedented speed of convergence and precision, and used it to determine with sub-Angstrom resolution the complete atomic structure of epitaxial La{sub 2-x}Sr{sub x}CuO{sub 4} ultrathin films. We focus on superconducting heterostructures built from constituent materials that are not superconducting in bulk samples. Single-phase metallic or superconducting films are also studied for comparison. The results show that this phase-retrieval diffraction method enables accurate measurement of structural modifications in near-surface layers, which may be critically important for elucidation of surface-sensitive experiments. Specifically we find that, while the copper-apical-oxygen distance remains approximately constant inmore » single-phase films, it shows a dramatic increase from the metallic-insulating interface of the bilayer towards the surface by as much as 0.45 {angstrom}. The apical-oxygen displacement is known to have a profound effect on the superconducting transition temperature.« less

Research on plasma and saliva levels of some bivalent cations in patients with chronic periodontitis (salivary cations in chronic periodontitis).

PubMed

Manea, A; Nechifor, M

2014-01-01

The purpose of this study was to determine whether chronic periodontitis can stand behind modifications in the salivary and blood concentration of some bivalent cations (Calcium, Magnesium, Zinc and Copper). For this purpose, we formed a group of 30 adult patients with clinically onset chronic periodontitis, and another one of 30 healthy patients as control. Both groups were free from acute oral pathology and general illnesses. The groups were divided again according to the habit of smoking. Total saliva samples were obtained as "first time in the morning", then weighed and processed. Cations were read on Atomic Absorption Spectrophotometer and by Ion Chromatography (Magnesium). The same patients were required to undergo laboratory blood tests for Calcium, Magnesium and Zinc. Data obtained was normalised, then statistically interpreted using two-tailed heteroscedastic t-Student tests. Our data confirmed the existence of a connection between salivary calcium, magnesium, zinc and copper, and of blood magnesium, and chronic periodontitis. Salivary calcium and magnesium are affected by smoking.

Identification and partial characterization of a low affinity metal-binding site in the light chain of tetanus toxin.

PubMed

Wright, J F; Pernollet, M; Reboul, A; Aude, C; Colomb, M G

1992-05-05

Tetanus toxin was shown to contain a metal-binding site for zinc and copper. Equilibrium dialysis binding experiments using 65Zn indicated an association constant of 9-15 microM, with one zinc-binding site/toxin molecule. The zinc-binding site was localized to the toxin light chain as determined by binding of 65Zn to the light chain but not to the heavy chain after separation by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and transfer to Immobilon membranes. Copper was an efficient inhibitor of 65Zn binding to tetanus toxin and caused two peptide bond cleavages in the toxin light chain in the presence of ascorbate. These metal-catalyzed oxidative cleavages were inhibited by the presence of zinc. Partial characterization of metal-catalyzed oxidative modifications of a peptide based on a putative metal-binding site (HELIH) in the toxin light chain was used to map the metal-binding site in the protein.

Modification of soil microbial activity and several hydrolases in a forest soil artificially contaminated with copper

NASA Astrophysics Data System (ADS)

Bellas, Rosa; Leirós, Mā Carmen; Gil-Sotres, Fernando; Trasar-Cepeda, Carmen

2010-05-01

Soils have long been exposed to the adverse effects of human activities, which negatively affect soil biological activity. As a result of their functions and ubiquitous presence microorganisms can serve as environmental indicators of soil pollution. Some features of soil microorganisms, such as the microbial biomass size, respiration rate, and enzyme activity are often used as bioindicators of the ecotoxicity of heavy metals. Although copper is essential for microorganisms, excessive concentrations have a negative influence on processes mediated by microorganisms. In this study we measured the response of some microbial indicators to Cu pollution in a forest soil, with the aim of evaluating their potential for predicting Cu contamination. Samples of an Ah horizon from a forest soil under oakwood vegetation (Quercus robur L.) were contaminated in the laboratory with copper added at different doses (0, 120, 360, 1080 and 3240 mg kg-1) as CuCl2×2H2O. The soil samples were kept for 7 days at 25 °C and at a moisture content corresponding to the water holding capacity, and thereafter were analysed for carbon and nitrogen mineralization capacity, microbial biomass C, seed germination and root elongation tests, and for urease, phosphomonoesterase, catalase and ß-glucosidase activities. In addition, carbon mineralization kinetics were studied, by plotting the log of residual C against incubation time, and the metabolic coefficient, qCO2, was estimated. Both organic carbon and nitrogen mineralization were lower in polluted samples, with the greatest decrease observed in the sample contaminated with 1080 mg kg-1. In all samples carbon mineralization followed first order kinetics; the C mineralization constant was lower in contaminated than in uncontaminated samples and, in general, decreased with increasing doses of copper. Moreover, it appears that copper contamination not only reduced the N mineralization capacity, but also modified the N mineralization process, since in the contaminated samples all of the inorganic nitrogen was present as ammonium, probably because of inhibition of nitrification. There was a marked decrease in biomass-C with addition of copper, and the decrease was more acute at intermediate doses (average decrease, 73%). Despite the decreases in microbial biomass and mineralized C, the value of qCO2 increased after the addition of copper. Urease activity was strongly affected by the presence of copper and the decrease was proportional to the dose; the activity at the highest dose was only 96% of that in the uncontaminated sample. Phosphomonoesterase activity was also affected by addition of copper; the reduction in activity was less than for urease and the greatest reduction was observed for the dose of 1080 mg kg-1 of copper. Catalase activity was affected by the contamination, but no clear trend was observed in relation to the dose of copper. ß-glucosidase was scarcely modified by the contamination but an increase in activity was observed at the highest dose of copper. Seed germination was not affected by copper contamination, since it only showed a clear decrease for the sample contaminated with the highest dose of copper, while root elongation decreased sharply with doses higher than 120 mg kg-1 of copper. The combined germination-elongation index followed a similar pattern to that of root elongation. For all investigated properties showing a reduction of more than 50%, the response to copper contamination was fitted to a sigmoidal dose-response model, in order to estimate the ED50 values. The ED50 values were calculated for microbial biomass, urease, root elongation and germination-elongation index, and similar values were obtained, ranging from 340 to 405 mg kg-1 Cu. The ED50 values may therefore provide a good estimation of soil deterioration.

Ferromagnetic coupling by spin polarization in a trinuclear copper(II) metallacyclophane with a triangular cage-like structure.

PubMed

Dul, Marie-Claire; Ottenwaelder, Xavier; Pardo, Emilio; Lescouëzec, Rodrigue; Journaux, Yves; Chamoreau, Lise-Marie; Ruiz-García, Rafael; Cano, Joan; Julve, Miguel; Lloret, Francesc

2009-06-15

A series of trinuclear copper(II) complexes of general formula A(6)[Cu(3)L(2)] x nH(2)O [L = benzene-1,3,5-tris(oxamate); A = Li(+) (n = 8), 1a; Na(+) (n = 11.5), 1b; and K(+) (n = 8.5), 1c] have been synthesized, and they have been structurally and magnetically characterized. X-ray diffraction on single crystals of 1c shows the presence of three square-planar copper(II)-bis(oxamato) moieties which are connected by a double benzene-1,3,5-triyl skeleton to give a unique metallacyclophane-type triangular cage. The copper basal planes are virtually orthogonal to the two benzene rings, which adopt an almost perfect face-to-face alignment. Complexes 1a-c exhibit a quartet (S = 3/2) ground spin state resulting from the moderate ferromagnetic coupling (J values in the range of +7.3 to +16.5 cm(-1)) between the three Cu(II) ions across the two benzene-1,3,5-tris(amidate) bridges [H = -J(S(1) x S(2) + S(2) x S(3) + S(3) x S(1)) with S(1) = S(2) = S(3) = S(Cu) = 1/2]. Density functional theory calculations on the S = 3/2 Cu(II)(3) ground spin state of 1c support the occurrence of a spin polarization mechanism for the propagation of the exchange interaction, as evidenced by the sign alternation of the spin density in the 1,3,5-substituted benzene spacers.

Time-Series Measurements of Atmospheric and Oceanic CO2 and O2 in the Western Gulf of Maine

DTIC Science & Technology

2008-09-01

is 2 meters in diameter and 3.5 m tall with a Surlyn foam flotation collar (Gilman Corporation). The Surlyn foam was cut with two chines so that...the flotation in the lightweight foam, the buoy with full 978-1-4244-2620-1/08/$25.00 ©2008 IEEE Report Documentation Page Form ApprovedOMB No. 0704...deployments, necessitating routine servicing (buoy pulled on deck in good weather and cleaned) (Figure 8). Modifications to a 90/10 copper -nickel

Higher biomolecules yield in phytoplankton under copper exposure.

PubMed

Silva, Jaqueline Carmo; Echeveste, Pedro; Lombardi, Ana Teresa

2018-05-30

Copper is an important metal for industry, and its toxic threshold in natural ecosystems has increased since the industrial revolution. As an essential nutrient, it is required in minute amounts, being toxic in slightly increased concentrations, causing great biochemical transformation in microalgae. This study aimed at investigating the physiology of Scenedesmus quadricauda, a cosmopolitan species, exposed to copper concentrations including those that trigger intracellular biochemical modifications. The Cu exposure concentrations tested ranged from 0.1 to 25 µM, thus including environmentally important levels. Microalgae cultures were kept under controlled environmental conditions and monitored daily for cell density, in vivo chlorophyll a, and photosynthetic quantum yield (Φ M ). After 24 h growth, free Cu 2+ ions were determined, and after 96 h, cellular Cu concentration, total carbohydrates, proteins, lipids, and cell volume were determined. The results showed that both free Cu 2+ ions and cellular Cu increased with Cu increase in culture medium. Microalgae cell abundance and in vivo chlorophyll a were mostly affected at 2.5 µM Cu exposure (3.8 pg Cu cell -1 ) and above. Approximately 31% decrease of photosynthetic quantum yield was obtained at the highest Cu exposure concentration (25 µM; 25 pg Cu cell -1 ) in comparison with the control. However, at environmentally relevant copper concentrations (0.5 µM Cu; 0.4 pg Cu cell -1 ) cell volume increased in comparison with the control. Considering biomolecules accumulation per unit cell volume, the highest carbohydrates and proteins yield was obtained at 1.0 µM Cu (1.1 pg Cu cell -1 ), while for lipids higher Cu was necessary (2.5 µM Cu; 3.8 pg Cu cell -1 ). This study is a contribution to the understanding of the effects of environmentally significant copper concentrations in the physiology of S. quadricauda, as well as to biotechnological approach to increase biomolecule yield in microalgae production. Copyright © 2018 Elsevier Inc. All rights reserved.

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

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

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

2015-12-21

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

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

PubMed Central

Elvington, Mark C.; Taylor-Pashow, Kathryn M. L.; Tosten, Michael H.; Hobbs, David T.

2016-01-01

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150 nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide. PMID:26967828

Influence of aminosilane precursor concentration on physicochemical properties of composite Nafion membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Kondratenko, Mikhail S.; Karpushkin, Evgeny A.; Gvozdik, Nataliya A.; Gallyamov, Marat O.; Stevenson, Keith J.; Sergeyev, Vladimir G.

2017-02-01

A series of composite proton-exchange membranes have been prepared via sol-gel modification of commercial Nafion membranes with [N-(2-aminoethyl)-3-aminopropyl]trimethoxysilane. The structure and physico-chemical properties (water uptake, ion-exchange capacity, vanadyl ion permeability, and proton conductivity) of the prepared composite membranes have been studied as a function of the precursor loading (degree of the membrane modification). If the amount of the precursor is below 0.4/1 M ratio of the amino groups of the precursor to the sulfonic groups of Nafion, the composite membranes exhibit decreased vanadium ion permeability while having relatively high proton conductivity. With respect to the use of a non-modified Nafion membrane, the performance of the composite membrane with an optimum precursor loading in a single-cell vanadium redox flow battery demonstrates enhanced energy efficiency in 20-80 mA cm-2 current density range. The maximum efficiency increase of 8% is observed at low current densities.

Water adsorption on surface-modified cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Wei, Zonghui; Sinko, Robert; Keten, Sinan; Luijten, Erik

Cellulose nanocrystals (CNCs) have attracted much attention as a filler phase for polymer nanocomposites due to their impressive mechanical properties, low cost, and environmental sustainability. Despite their promise for this application, there are still numerous obstacles that prevent optimal performance of CNC-polymer nanocomposites, such as poor filler dispersion and high levels of water absorption. One way to mitigate these negative effects is to modify CNC surfaces. Computational approaches can be utilized to obtain direct insight into the properties of modified CNC surfaces and probe the interactions of CNCs with other materials to facilitate the experimental design of nanocomposites. We use atomistic grand-canonical Monte Carlo simulations to study how surface modification of ion-exchanged sulfated cellulose nanocrystals (Na-CNCs) impacts water adsorption. We find that methyl(triphenyl)phosphonium-exchanged CNCs adsorb less water than Na-CNCs at the same relative humidity, supporting recent experimental dynamic vapor sorption measurements. By characterizing the distribution and configuration of water molecules near the modified CNC surfaces we determine how surface modifications disrupt CNC-water interactions.

Chain exchange in triblock copolymer micelles

NASA Astrophysics Data System (ADS)

Lu, Jie; Lodge, Timothy; Bates, Frank

2015-03-01

Block polymer micelles offer a host of technological applications including drug delivery, viscosity modification, toughening of plastics, and colloidal stabilization. Molecular exchange between micelles directly influences the stability, structure and access to an equilibrium state in such systems and this property recently has been shown to be extraordinarily sensitive to the core block molecular weight in diblock copolymers. The dependence of micelle chain exchange dynamics on molecular architecture has not been reported. The present work conclusively addresses this issue using time-resolved small-angle neutron scattering (TR-SANS) applied to complimentary S-EP-S and EP-S-EP triblock copolymers dissolved in squalane, a selective solvent for the EP blocks, where S and EP refer to poly(styrene) and poly(ethylenepropylene), respectively. Following the overall SANS intensity as a function of time from judiciously deuterium labelled polymer and solvent mixtures directly probes the rate of molecular exchange. Remarkably, the two triblocks display exchange rates that differ by approximately ten orders of magnitude, even though the solvophobic S blocks are of comparable size. This discovery is considered in the context of a model that successfully explains S-EP diblock exchange dynamics.

Synthesis, X-ray crystal structures, and phosphate ester cleavage properties of bis(2-pyridylmethyl)amine copper(II) complexes with guanidinium pendant groups.

PubMed

Belousoff, Matthew J; Tjioe, Linda; Graham, Bim; Spiccia, Leone

2008-10-06

Three new derivatives of bis(2-pyridylmethyl)amine (DPA) featuring ethylguanidinium (L (1)), propylguanidinium (L (2)), or butylguanidinium (L (3)) pendant groups have been prepared by the reaction of N, N- bis(2-pyridylmethyl)alkane-alpha,omega-diamines with 1 H-pyrazole-1-carboxamidine hydrochloride. The corresponding mononuclear copper(II) complexes were prepared by reacting the ligands with copper(II) nitrate and were isolated as [Cu(LH (+))(OH 2)](ClO 4) 3. xNaClO 4. yH 2O ( C1: L = L (1), x = 2, y = 3; C2: L = L (2), x = 2, y = 4; C3: L = L (3), x = 1, y = 0) following cation exchange purification. Recrystallization yielded crystals of composition [Cu(LH (+))(X)](ClO 4) 3.X ( C1': L = L (1), X = MeOH; C2': L = L (2), X = H 2O; C3': L = L (3), X = H 2O), which were suitable for X-ray crystallography. The crystal structures of C1', C2', and C3' indicate that the DPA moieties of the ligands coordinate to the copper(II) centers in a meridional fashion, with a water or methanol molecule occupying the fourth basal position. Weakly bound perchlorate anions located in the axial positions complete the distorted octahedral coordination spheres. The noncoordinating, monoprotonated guanidinium groups project away from the Cu(II)-DPA units and are involved in extensive charge-assisted hydrogen-bonding interactions with cocrystallized water/methanol molecules and perchlorate anions within the crystal lattices. The copper(II) complexes were tested for their ability to promote the cleavage of two model phosphodiesters, bis( p-nitrophenyl)phosphate (BNPP) and uridine-3'- p-nitrophenylphosphate (UpNP), as well as supercoiled plasmid DNA (pBR 322). While the presence of the guanidine pendants was found to be detrimental to BNPP cleavage efficiency, the functionalized complexes were found to cleave plasmid DNA and, in some cases, the model ribose phosphate diester, UpNP, at a faster rate than the parent copper(II) complex of DPA.

Chelant extraction of heavy metals from contaminated soils.

PubMed

Peters, R W

1999-04-23

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction, the soil was successfully treated passing both the Toxicity Characteristics Leaching Procedure (TCLP) and EPA Total Extractable Metal Limit. The final residual Pb concentration was about 300 mg/kg, with a corresponding TCLP of 1.5 mg/l. Removal of the exchangeable and carbonate fractions for Cu and Zn was achieved during the first extraction stage, whereas it required two extraction stages for the same fractions for Pb. Removal of Pb, Cu, and Zn present as exchangeable, carbonates, and reducible oxides occurred between the fourth- and fifth-stage extractions. The overall removal of copper, lead, and zinc from the multiple-stage washing were 98.9%, 98.9%, and 97.2%, respectively. The concentration and operating conditions for the soil washing extractions were not necessarily optimized. If the conditions had been optimized and using a more representative Pb concentration (approximately 12000 mg/kg), it is likely that the TCLP and residual heavy metal soil concentrations could be achieved within two to three extractions. The results indicate that the J-Field contaminated soils can be successfully treated using a soil washing technique. Copyright 1999 Published by Elsevier Science B.V.

Ligand effects on the structure and magnetic properties of alternating copper(II) chains with 2,2'-bipyrimidine- and polymethyl-substituted pyrazolates as bridging ligands.

PubMed

Castro, Isabel; Calatayud, M Luisa; Barros, Wdeson P; Carranza, José; Julve, Miguel; Lloret, Francesc; Marino, Nadia; De Munno, Giovanni

2014-06-02

A novel series of heteroleptic copper(II) compounds of formulas {[Cu2(μ-H2O)(μ-pz)2(μ-bpm)(ClO4)(H2O)]ClO4·2H2O}n (1), {[Cu2(μ-H2O)(μ-3-Mepz)2(μ-bpm)](ClO4)2·2H2O}n (2), and {[Cu2(μ-OH)(μ-3,5-Me2pz)(μ-bpm)(H-3,5-Me2pz)2](ClO4)2}n (3) [bpm = 2,2'-bipyrimidine, Hpz = pyrazole, H-3-Mepz = 3-methylpyrazole, and H-3,5-Me2pz = 3,5-dimethylpyrazole] have been synthesized and structurally characterized by X-ray diffraction methods. The crystal structures of 1 and 2 consist of copper(II) chains with regular alternating bpm and bis(pyrazolate)(aqua) bridges, whereas that of 3 is made up of copper(II) chains with regular alternating bpm and (pyrazolate)(hydroxo) bridges. The copper centers are six- (1) or five-coordinate (2) in axially elongated, octahedral (1) or square-pyramidal (2) environments in 1 and 2, whereas they are five-coordinate in distorted trigonal-bipyramidal surroundings in 3. The values of the copper-copper separations across the bpm/pyrazolate bridges are 5.5442(7)/3.3131(6) (1), 5.538(1)/3.235(1) (2), and 5.7673(7)/3.3220(6) Å (3). The magnetic properties of 1-3 have been investigated in the temperature range of 25-300 K. The analysis of their magnetic susceptibility data through the isotropic Hamiltonian for an alternating antiferromagnetic copper(II) chain model [H = -J∑i=1-n/2 (S2i·S2i-1 + αS2i·S2i+1), with α = J'/J and Si = SCu = 1/2] reveals the presence of a strong to moderate antiferromagnetic coupling through the bis(pyrazolate)(aqua) [-J = 217 (1) and 215 cm(-1) (2)] and (pyrazolate)(hydroxo) bridges [-J = 153 cm(-1) (3)], respectively, whereas a strong to weak antiferromagnetic coupling occurs through the bis-bidentate bpm [-J' = 211 (1), 213 (2), and 44 cm(-1) (3)]. A simple orbital analysis of the magnetic exchange interaction within the bpm- and pyrazolate-bridged dicopper(II) fragments of 1-3 visualizes the σ-type pathways involving the (dx(2)-y(2)) (1 and 2) or d(z(2)) (3) magnetic orbitals on each metal ion, which account for the variation of the magnetic properties in these three novel examples of one-dimensional copper(II) compounds with regular alternating intrachain antiferromagnetic interactions.

Study and modification of the reactivity of carbon fibers

NASA Technical Reports Server (NTRS)

Walker, P. L., Jr.; Ismail, I. M.; Mahajan, O. P.; Eapen, T. A.

1980-01-01

The reactivity to air of polyactylonitrile-based carbon fiber cloth was enhanced by the addition of metals to the cloth. The cloth was oxidized in 54 wt% nitric acid in order to increase the surface area of the cloth and to add carbonyl groups to the surface. Metal addition was then achieved by soaking the cloth in metal acetate solution to effect exchange between the metal carbon and hydrogen on the carbonyl groups. The addition of potassium, sodium, calcium and barium enhanced fiber cloth reactivity to air at 573 K. Extended studies using potassium addition showed that success in enhancing fiber cloth reactivity to air depends on: extent of cloth oxidation in nitric acid, time of exchange in potassium acetate solution and the thoroughness of removing metal acetate from the fiber pore structure following exchange. Cloth reactivity increases essentially linearly with increase in potassium addition via exchange.

Development and fabrication of a diffusion welded Columbium alloy heat exchanger. [for space power generation

NASA Technical Reports Server (NTRS)

Zimmerman, W. F.; Duderstadt, E. C.; Wein, D.; Titran, R. H.

1978-01-01

A Mini Brayton space power generation system required the development of a Columbium alloy heat exchanger to transfer heat from a radioisotope heat source to a He/Xe working fluid. A light-weight design featured the simultaneous diffusion welding of 148 longitudinal fins in an annular heat exchanger about 9-1/2 in. in diameter, 13-1/2 in. in length and 1/4 in. in radial thickness. To complete the heat exchanger, additional gas ducting elements and attachment supports were added by GTA welding in a vacuum-purged inert atmosphere welding chamber. The development required the modification of an existing large size hot isostatic press to achieve HIP capabilities of 2800 F and 10,000 psi for at least 3 hr. Excellent diffusion welds were achieved in a high-quality component which met all system requirements.

Purification and characterization of RNA allied extracellular tyrosinase from Aspergillus species.

PubMed

Inamdar, Shrirang; Joshi, Swati; Bapat, Vishwas; Jadhav, Jyoti

2014-02-01

Production of L-DOPA, an anti-Parkinson's drug, using biological sources is widely studied in which tyrosinase is known to play a vital role. Tyrosinase is an omnipresent type 3 copper enzyme participating in many essential biological functions. Understanding properties of tyrosinase is essential for developing useful tyrosinase-based applications. Hence, extracellular tyrosinase from Aspergillus flavus UWFP 570 was purified using ammonium sulphate precipitation and DEAE ion exchange chromatography up to 8.3-fold. Purified protein was a riboprotein in nature containing significant amount of RNA which was confirmed colorimetrically and by electrophoresis. Removal of RNA reduced the activity and altered the conformation of tyrosinase as suggested by spectroflurometric results. Optimum pH and temperature of this 140 kDa protein were 7 and 40 °C, respectively. Copper sulphate and magnesium chloride enhanced the activity whereas in contrast FeCl₃ inhibited the activity completely. Purified tyrosinase transformed L-tyrosine (5 mM) to L-DOPA within 5 h.

Chemistry in Confinement: Copper and Palladium Catalyzed Ecofriendly Organic Transformations within Porous Frameworks.

PubMed

Kumar, Basuvaraj Suresh; Pitchumani, Kasi

2018-05-01

A concise account on the use of transition metals copper (Cu) and palladium (Pd), as their cations as well as nanoparticles exchanged/immobilized onto porous frameworks such as zeolites, metal organic frameworks (MOFs), covalent organic polymers (COPs) and hollow nanostructures, functioning as catalysts in organic synthesis is presented. This biomimetic account, "focusing on catalytic systems in confinement" within zero-dimensional microenvironments and second sphere coordination covers primarily results from our group on N-sulfonylketenimine mediated cycloaddition, hydrogenation and C-C bond forming reactions, thus providing an interesting insight into the versatility and utility of these Cu and Pd catalysts. Other significant advantages and green credentials of confinement such as stability, selectivity, reusability, promotion of multicomponent reactions, use of green solvents, atom economy, and use of ambient conditions are highlighted at appropriate places. In the final section, our views on the current achievements and the future prospects in this area are summarized. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterization and tin/copper-nitrogen substitutional effect on photocatalytic activity of honeycomb ordered P2-Na2Ni2TeO6

NASA Astrophysics Data System (ADS)

Kadari, Ramaswamy; Velchuri, Radha; Sreenu, K.; Ravi, Gundeboina; Munirathnam, Nagegownivari R.; Vithal, Muga

2016-11-01

We have successfully prepared visible light active tin/copper-nitrogen co-doped honeycomb ordered P2-Na2Ni2TeO6 photocatalysts by solid state/ion exchange methods. Powder XRD, TG analysis, SEM, surface area, O-N-H analysis, ICP-OES, FT-IR and UV-DRS measurements are employed to characterize all the samples. All the doped compositions adopted hexagonal lattice with space group P63/mcm. The photocatalytic activity of all the samples was studied against the degradation of methyl violet (MV) and methylene blue (MB) under visible light irradiation. The variation of the photocatalytic activity due to the substitution of cation, anion and co-doping in Na2Ni2TeO6 is investigated. Co-doped samples have exhibited higher activity compared to rest of the materials. The role of reactive intermediate species in the photocatalytic degradation of dyes is also studied using appropriate scavengers.

Antimicrobial Polymers with Metal Nanoparticles

PubMed Central

Palza, Humberto

2015-01-01

Metals, such as copper and silver, can be extremely toxic to bacteria at exceptionally low concentrations. Because of this biocidal activity, metals have been widely used as antimicrobial agents in a multitude of applications related with agriculture, healthcare, and the industry in general. Unlike other antimicrobial agents, metals are stable under conditions currently found in the industry allowing their use as additives. Today these metal based additives are found as: particles, ions absorbed/exchanged in different carriers, salts, hybrid structures, etc. One recent route to further extend the antimicrobial applications of these metals is by their incorporation as nanoparticles into polymer matrices. These polymer/metal nanocomposites can be prepared by several routes such as in situ synthesis of the nanoparticle within a hydrogel or direct addition of the metal nanofiller into a thermoplastic matrix. The objective of the present review is to show examples of polymer/metal composites designed to have antimicrobial activities, with a special focus on copper and silver metal nanoparticles and their mechanisms. PMID:25607734

Sequential Extraction Results and Mineralogy of Mine Waste and Stream Sediments Associated With Metal Mines in Vermont, Maine, and New Zealand

USGS Publications Warehouse

Piatak, N.M.; Seal, R.R.; Sanzolone, R.F.; Lamothe, P.J.; Brown, Z.A.; Adams, M.

2007-01-01

We report results from sequential extraction experiments and the quantitative mineralogy for samples of stream sediments and mine wastes collected from metal mines. Samples were from the Elizabeth, Ely Copper, and Pike Hill Copper mines in Vermont, the Callahan Mine in Maine, and the Martha Mine in New Zealand. The extraction technique targeted the following operationally defined fractions and solid-phase forms: (1) soluble, adsorbed, and exchangeable fractions; (2) carbonates; (3) organic material; (4) amorphous iron- and aluminum-hydroxides and crystalline manganese-oxides; (5) crystalline iron-oxides; (6) sulfides and selenides; and (7) residual material. For most elements, the sum of an element from all extractions steps correlated well with the original unleached concentration. Also, the quantitative mineralogy of the original material compared to that of the residues from two extraction steps gave insight into the effectiveness of reagents at dissolving targeted phases. The data are presented here with minimal interpretation or discussion and further analyses and interpretation will be presented elsewhere.

Dye house wastewater treatment through advanced oxidation process using Cu-exchanged Y zeolite: a heterogeneous catalytic approach.

PubMed

Fathima, Nishtar Nishad; Aravindhan, Rathinam; Rao, Jonnalagadda Raghava; Nair, Balachandran Unni

2008-01-01

Catalytic wet hydrogen peroxide oxidation of an anionic dye has been explored in this study. Copper(II) complex of NN'-ethylene bis(salicylidene-aminato) (salenH2) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by Fourier transforms infra red spectroscopy, X-ray powder diffractograms, Thermo-gravimetric and differential thermal analysis and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that complete removal of color has been obtained after a period of less than 1h at 60 degrees C, 0.175M H2O2 and 0.3g l(-1) catalyst. More than 95% dye removal has been achieved using this catalyst for commercial effluent. These studies indicate that copper salen complex encapsulated in zeolite framework is a potential heterogeneous catalyst for removal of color from wastewaters.

The role of mineral surface chemistry in modified dextrin adsorption.

PubMed

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

2011-05-15

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

Trialkylphosphine-stabilized copper(I) gallium(III) phenylchalcogenolate complexes: crystal structures and generation of ternary semiconductors by thermolysis.

PubMed

Kluge, Oliver; Krautscheid, Harald

2012-06-18

A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R(3)P)(m)Cu(n)Me(2-x)Ga(EPh)(n+x+1)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te; x = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis. The Ga-E bonds are relatively rigid, in contrast to flexible Cu-E bonds. The lengths of the latter are controlled by the coordination number and steric influences. The Ga-E bond lengths depend systematically on the number of methyl groups bound to the gallium atom, with somewhat shorter bonds in monomethyl compounds compared to dimethyl compounds. Quantum chemical computations reproduce this trend and show furthermore that the rotation of one phenyl group around the Ga-E bond is a low energy process with two distinct minima, corresponding to two different conformations found experimentally. Mixtures of different types of chalcogen atoms on molecular scale are possible, and then ligand exchange reactions in solution lead to mixed site occupation. In thermogravimetric studies the complexes were converted into the ternary semiconductors CuGaE(2). The thermolysis reaction is completed at temperatures between 250 and 400 °C, typically with lower temperatures for the heavier chalcogens. Because of significant release of Me(3)Ga during the thermolysis process, and especially in case of copper excess in the precursor complexes, binary copper chalcogenides are obtained as additional thermolysis products. Quaternary semiconductors can be obtained from mixed chalcogen precursors.

Novel alkaline earth copper germanates with ferro and antiferromagnetic S=1/2 chains

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

Brandao, Paula; Reis, Mario S; Gai, Zheng

Two new alkaline earth copper(II) germanates were hydrothermally synthesized: CaCuGeO4 center dot H2O (1) and BaCu2Ge3O9 center dot H2O (2), and their structures determined by single crystal X-ray diffraction. Compound (1) crystallizes in space group P2(1)/c with a=5.1320(2) angstrom, b=16.1637(5) angstrom, c=5.4818(2) angstrom, beta=102.609(2)degrees, V=443.76(3) angstrom(3) and Z=4. This copper germanate contains layers of composition [CuGeO4](infinity)(2-) comprising CuO4 square planes and GeO4 tetrahedra with calcium and water molecules in the inter-layer space. Compound (2) crystallizes in the Cmcm space group with a=5.5593(3) angstrom, b=10.8606(9) angstrom, c=13.5409(8) angstrom, V=817.56(9) angstrom(3) and Z=4. This structure contains GeO6 and CuO6 octahedra as wellmore » as GeO4 tetrahedra, forming a three-dimensional network of interconnecting six-membered ring channels. The magnetic susceptibility for both samples can be interpreted as S=1/2 chains, in agreement with the copper topology observed in the crystal structure. The susceptibility of (1) exhibits a Bonner-Fisher type behavior, resulting from antiferromagnetic intra-chain interactions without three-dimensional ordering down to 5 K-the lowest measured temperature. This observation, together with the absence of super-exchange paths between the copper chains, make this system particularly promising for the study of low dimensional magnetism. The magnetic properties of (2) show a very weak ferromagnetic near-neighbor interaction along the chain. In this compound a peak the chi T plot seems to indicate the onset of interchain antiferromagentic correlations. However, no ordering temperature is detected in the susceptibility data.« less

Antimicrobial properties of zeolite-X and zeolite-A ion-exchanged with silver, copper, and zinc against a broad range of microorganisms.

PubMed

Demirci, Selami; Ustaoğlu, Zeynep; Yılmazer, Gonca Altın; Sahin, Fikrettin; Baç, Nurcan

2014-02-01

Zeolites are nanoporous alumina silicates composed of silicon, aluminum, and oxygen in a framework with cations, water within pores. Their cation contents can be exchanged with monovalent or divalent ions. In the present study, the antimicrobial (antibacterial, anticandidal, and antifungal) properties of zeolite type X and A, with different Al/Si ratio, ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions were investigated individually. The study presents the synthesis and manufacture of four different zeolite types characterized by scanning electron microscopy and X-ray diffraction. The ion loading capacity of the zeolites was examined and compared with the antimicrobial characteristics against a broad range of microorganisms including bacteria, yeast, and mold. It was observed that Ag(+) ion-loaded zeolites exhibited more antibacterial activity with respect to other metal ion-embedded zeolite samples. The results clearly support that various synthetic zeolites can be ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions to acquire antimicrobial properties or ion-releasing characteristics to provide prolonged or stronger activity. The current study suggested that zeolite formulations could be combined with various materials used in manufacturing medical devices, surfaces, textiles, or household items where antimicrobial properties are required.

Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties.

PubMed

Grancha, Thais; Acosta, Alvaro; Cano, Joan; Ferrando-Soria, Jesús; Seoane, Beatriz; Gascon, Jorge; Pasán, Jorge; Armentano, Donatella; Pardo, Emilio

2015-11-16

We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.

Comments on cathode contaminants and the LBNL test stand

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

Bieniosek, F.; Baca, D.; Greenway, W.

This report collects information on cathode contaminants we have gathered in the process of operating the LBNL DARHT cathode test stand. Information on contaminants is compiled from several sources. The attachment, ''Practical Aspects of Modern Dispenser Cathodes'', is from Heat Wave Corp. (TB-134) and was originally published in Microwave Journal, September 1979. Cathode contamination depends on both material choices and residual gases. Table 1 of TB-134 lists materials that can poison dispenser cathodes. These include reactive residual gases or vapors such as oxygen, water vapor, benzene, chlorine, fluorine, sulfur, silicon, and most metals other than molybdenum, rhenium, tungsten, and copper.more » The metals interact with the cathode surface through their vapor pressure. A paper by Nexsen and Turner, J. Appl. Phys. 68, 298-303 (1990) shows the threshold effects of some common residual gases or vapors on cathode performance. The book by Walter H. Kohl, Handbook of Materials and Techniques for Vacuum Devices, also contains useful information on cathodes and poisoning agents. A plot of the vapor pressures and poisoning effect of certain metals (from Kohl) is shown below. Note that the vapor pressure of zinc is 1.1 x 10{sup -8} Torr at 400 K = 127 C, and 2.7 x 10{sup -5} at 500 K = 227 C. By contrast iron reaches a vapor pressure 1 x 10{sup -8} between 800 and 900 C. Therefore it is important to eliminate any brass parts that could exceed a temperature of 100 C. Many structural components of the cathode assembly contain steel. At 500-600 C in an oxygen atmosphere chromium oxide may outgas from the steel. [Cho, et.al., J. Vac. Sci. Technol. A 19, p. 998 (2001)]. Steel may also contain silicon, and sulfur at low concentrations. Therefore use of steel should be limited or avoided at high temperature near the cathode. Materials that should be avoided in the vicinity of the cathode include brass, silver, zinc, non-OFHC copper, silicates, and sulfur-containing lubricants such molybdenum disulfide. Macor is an aluminosilicate-based insulator that is not stable at high temperature. Macor near the cathode should be replaced by a high-temperature insulator such as alumina ceramic. Other insulating materials that contain silicates, such as fiber insulating sleeves, should be avoided. Copper that is not OFHC contains oxygen and other impurities and should be avoided. Lubricating screw coatings should be chosen carefully to have no sulfur content. Common sources of contamination that can cause low emission include water, saliva, silicates such as glass dust, etc. Cathodes should be handled in near clean-room conditions to minimize the amount of water vapor on the cathode surface from breathing, etc. Cathodes should also be stored in such as a way as to avoid contact with materials such as glass dust and water vapor. Attached are plots of SEM data for several test pieces that were taken from the LBNL test stand after activation of the 311x scandate DARHT cathode. Several copper pieces in the anode region were tested, showing the presence of zinc. Two stainless steel nuts coated with a contaminant were also tested. The SEM data indicates the presence of zinc and some sulfur. The zinc has been traced to a brass piece, and the sulfur to the possible use of molybdenum disulfide lubricant on a nut in the system. Finally a swipe of contaminant on the vacuum vessel wall analyzed by a commercial testing laboratory shows again the presence of zinc. In order to improve system cleanliness, we have implemented the following modifications to the test stand: replaced the brass piece with copper-tungsten; replaced Macor insulators with alumina ceramic; used boron nitride lubricant; replaced copper beam stop with OFHC copper; and replaced steel pieces near the cathode where possible with copper or copper-tungsten. A clean fire of high-temperature components and a high-current filament test have shown no evidence to date for contaminants since the modifications.« less

Chemical modification of corn fiber with ion-exchanging groups

USDA-ARS?s Scientific Manuscript database

Pretreated corn fiber was chemically modified with quaternary ammonium group or/and sulfonated with 3-chloro-2-hydroxypropanesulfonic acid under vacuum or at ambient pressure. The soluble fraction was dialyzed through 1 kDa MWCO dialysis tubing and the material retained inside the tubing was filtere...

76 FR 1063 - Modifications of Debt Instruments

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-07

... modified instrument received in an exchange will be classified as debt for Federal income tax purposes... properly classified as debt for Federal income tax purposes. Effective/Applicability Date The regulations... right that is not debt for federal income tax purposes. Paragraph (g) of this section contains examples...

17 CFR 9.5 - Motions.

Code of Federal Regulations, 2010 CFR

2010-04-01

... DISCIPLINARY, ACCESS DENIAL OR OTHER ADVERSE ACTIONS General Provisions § 9.5 Motions. (a) In general. An... request reconsideration, vacation or modification of the action. (d) Dilatory motions. Frivolous or... 17 Commodity and Securities Exchanges 1 2010-04-01 2010-04-01 false Motions. 9.5 Section 9.5...

17 CFR 9.5 - Motions.

Code of Federal Regulations, 2011 CFR

2011-04-01

... DISCIPLINARY, ACCESS DENIAL OR OTHER ADVERSE ACTIONS General Provisions § 9.5 Motions. (a) In general. An... request reconsideration, vacation or modification of the action. (d) Dilatory motions. Frivolous or... 17 Commodity and Securities Exchanges 1 2011-04-01 2011-04-01 false Motions. 9.5 Section 9.5...

Laccase of Cyathus bulleri: structural, catalytic characterization and expression in Escherichia coli.

PubMed

Salony; Garg, N; Baranwal, R; Chhabra, M; Mishra, S; Chaudhuri, T K; Bisaria, V S

2008-02-01

Cyathus bulleri, a ligninolytic fungus, produces a single laccase the internal peptides (3) of which bear similarity to laccases of several white rot fungi. Comparison of the total amino acid composition of this laccase with several fungal laccases indicated dissimilarity in the proportion of some basic and hydrophobic amino acids. Analysis of the circular dichroism spectrum of the protein indicated 37% alpha-helical, 26% beta-sheet and 38% random coil content which differed significantly from that in the solved structures of other laccases, which contain higher beta-sheet structures. The critical role of the carboxylic group containing amino acids was demonstrated by determining the kinetic parameters at different pH and this was confirmed by the observation that a critical Asp is strongly conserved in both Ascomycete and Basidiomycete laccases. The enzyme was denatured in the presence of a number of denaturing agents and refolded back to functional state with copper. In the folding experiments under alkaline conditions, zinc could replace copper in restoring 100% of laccase activity indicating the non-essential role of copper in this laccase. The laccase was expressed in Escherichia coli by a modification of the ligation-anchored PCR approach making it the first fungal laccase to be expressed in a bacterial host. The laccase sequence was confirmed by way of analysis of a 435 bp sequence of the insert.

Plasma impact on structural, morphological and optical properties of copper acetylacetonate thin films

NASA Astrophysics Data System (ADS)

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

2018-06-01

The influence of plasma exposure on structural, morphological and optical properties of copper (II) acetylacetonate thin films deposited by thermal evaporation technique was investigated. Copper (II) acetylacetonate as-grown thin films were exposed to the atmospheric plasma for different times. The exposure of as-grown cu(acac)2 thin film to atmospheric plasma for 5 min modified its structural, morphological and optical properties. The effect of plasma exposure on structure and roughness of cu(acac)2 thin films was evaluated by XRD and AFM techniques, respectively. The XRD results showed an increment in crystallinity due to exposure for 5 min, but, when the exposure time reaches 10 min, the film was transformed to an amorphous state. The AFM results revealed a strong modification of films roughness when the average roughness decreased from 63.35 nm to 1 nm as a result of interaction with plasma. The optical properties of as-grown and plasma exposured cu(acac)2 thin films were studied using spectrophotometric method. The exposure of cu(acac)2 thin films to plasma produced the indirect energy gap decrease from 3.20 eV to 2.67 eV for 10 min exposure time. The dispersion parameters were evaluated in terms of single oscillator model for as-grown and plasma exposured thin films. The influence of plasma exposure on third order optical susceptibility was studied.

Aminosilanization nanoadhesive layer for nanoelectric circuits with porous ultralow dielectric film.

PubMed

Zhao, Zhongkai; He, Yongyong; Yang, Haifang; Qu, Xinping; Lu, Xinchun; Luo, Jianbin

2013-07-10

An ultrathin layer is investigated for its potential application of replacing conventional diffusion barriers and promoting interface adhesion for nanoelectric circuits with porous ultralow dielectrics. The porous ultralow dielectric (k ≈ 2.5) substrate is silanized by 3-aminopropyltrimethoxysilane (APTMS) to form the nanoadhesive layer by performing oxygen plasma modification and tailoring the silanization conditions appropriately. The high primary amine content is obtained in favor of strong interaction between amino groups and copper. And the results of leakage current measurements of metal-oxide-semiconductor capacitor structure demonstrate that the aminosilanization nanoadhesive layer can block copper diffusion effectively and guarantee the performance of devices. Furthermore, the results of four-point bending tests indicate that the nanoadhesive layer with monolayer structure can provide the satisfactory interface toughness up to 6.7 ± 0.5 J/m(2) for Cu/ultralow-k interface. Additionally, an annealing-enhanced interface toughness effect occurs because of the formation of Cu-N bonding and siloxane bridges below 500 °C. However, the interface is weakened on account of the oxidization of amines and copper as well as the breaking of Cu-N bonding above 500 °C. It is also found that APTMS nanoadhesive layer with multilayer structure provides relatively low interface toughness compared with monolayer structure, which is mainly correlated to the breaking of interlayer hydrogen bonding.