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Sample records for cu esr studies

  1. High-field ESR studies of the quantum spin magnet CaCu2O3

    NASA Astrophysics Data System (ADS)

    Goiran, M.; Costes, M.; Broto, J. M.; Chou, F. C.; Klingeler, R.; Arushanov, E.; Drechsler, S.-L.; Büchner, B.; Kataev, V.

    2006-05-01

    We report an electron spin resonance (ESR) study of the s = 1/2 Heisenberg pseudo-ladder magnet CaCu2O3 in pulsed magnetic fields up to 40 T. At sub-terahertz frequencies we observe an ESR signal originating from a small amount of uncompensated spins residing presumably at the imperfections of the strongly antiferromagnetically correlated host spin lattice. The data give evidence that these few per cent of 'extra' spin states are coupled strongly to the bulk spins and are involved in the antiferromagnetic (AF) ordering at TN = 25 K. By mapping the frequency/resonance field diagram we have determined a small gap for magnetic excitations below TN of the order of ~0.3 0.8 meV. Such a small value of the gap explains the occurrence of the spin-flop transition in CaCu2O3 at weak magnetic fields μ0Hsf ~ 3 T. Qualitative changes of the ESR response with the increasing field strength give indications that strong magnetic fields reduce the AF correlations and may even suppress the long-range magnetic order in CaCu2O3. ESR data support scenarios with a significant role of the 'extra' spin states for the properties of low-dimensional quantum magnets.

  2. IR and ESR studies on novel Cu(II) theophyllinato complexes containing mono- or bidentate ligands

    NASA Astrophysics Data System (ADS)

    Forizs, Edit; David, L.; Cozar, O.; Chiş, V.; Damian, G.; Csibi, Jolán

    1999-05-01

    Three mixed-ligand copper(II) complexes containing theophylline and mono- or bidentate N-donor ligands (2,2'-bipyridine, 4-fluoraniline and 1,10-phenanthroline) were synthesized and characterized by elemental analysis, IR and ESR spectra. According to IR and ESR data the Cu(II) complexes exhibit a distorted tetrahedral coordination of copper by two nitrogen atoms of the monodentate or bidentate ligands and the two monodentate theophyllinate anion bonded through N(7) atom.

  3. Microwave Absorption Studies on HIGH-Tc Superconductors and Related Materials VII — Esr of Dpph Coated on a Thin BiSrCaCuO Film Fabricated on MgO(100) Substrate

    NASA Astrophysics Data System (ADS)

    Sugawara, K.; Sugimoto, T.; Shiohara, Y.; Tanaka, S.

    ESR of DPPH coated on a Bi-Sr-Ca-Cu-O (BSCCO) film (350 Å thick) fabricated on MgO(100) substrate by MOCVD was studied. Temperature dependence of the ESR peak-to-peak linewidth, ΔHpp, and the effect of applied magnetic field on ΔHpp have been studied below about 100 K. The results were compared with those of ESR of DPPH coated on ceramic Y-Ba-Cu-O samples (powder and bulk) made by the MPMG method. The DPPH ESR for the BSCCO film revealed that ΔHpp was independent of applied magnetic field up to about 9 kG. In addition, no similarity between the temperature dependence of the excess ESR linewidth of the DPPH and that of critical current density was found for the BSCCO film. These results for the BSCCO film are different from those for the MPMG YBCO samples.

  4. ESR studies of Anatolian gypsum

    NASA Astrophysics Data System (ADS)

    Ulusoy, Ülkü

    2004-05-01

    Electron spin resonance (ESR) was used to date the formation and most recent recrystallization of three types of gypsum samples (massive, bedded and fracture filling gypsum) from the Sakarya Formation at Eskişehir in the middle of Turkey. The ESR spectra had the signals of Fe 3+ and Mn 2+ in addition to those of the G1 and G2 sensitive centers ( g=2.002 and 2.008) to artificial γ-irradiation. ESR intensities of G1 and G2 were enhanced by γ-ray irradiation to give equivalent doses DE for each sample. The ESR ages derived from the annual doses of 238U, 232Th and 40K contents of the samples determined by thermal neutron activation analysis (TNAA) were between 43±18 ka (massive gypsum) and 1100±466 ka (bedded gypsum) as minimal and maximal values. The ages fall into the upper Miocene-Pliocene Epoch of the geological time scale, which agreed with the stratigraphy.

  5. ESR experiments and spectra simulations in YBa2Cu3O7-x, Y2BaCuO5, and BaCuO2+x

    NASA Astrophysics Data System (ADS)

    de Mesquita, R. N.; Castilho, J. H.; Barberis, G. E.; Rettori, C.; Torriani, I.; de Lima, O. F.; Gama, S.; Jardim, R. F.; Terrile, M. C.; Basso, H.; Nascimento, O. R.

    1989-04-01

    Room-temperature X- and Q-band ESR spectra of the high-Tc superconductor YBa2Cu3O7-x and the semiconductors Y2BaCuO5 and BaCuO2+x are studied experimentally and theoretically by measuring, calculating, and fitting the powder spectra corresponding to an anisotropic Zeeman Hamiltonian for Cu2+ in orthorhombic and tetragonal local symmetries. ESR and x-ray studies in their correspoinding oxygen-deficient stoichiometries, obtained by heat treatment under vacuum, were also done. Our results support those of Bowden et al. and Vier et al. in RBa2Cu3O7-x (R=Y, Eu), indicating that the Cu(1) and Cu(2) atoms in the pure YBa2Cu3O7-x phase are not ESR active and the small resonance observed in these compounds comes from other residual phases. The purest YBa2Cu3O7-xsamples that we were able to prepare still have 0.1-0.5 % mass fraction of other residual copper compounds which are responsible for the observed resonance.

  6. Microwave Absorption Studies on HIGH-Tc Superconductors and Related Materials Iv:. Esr as a Probe of Flux Pinning in Y-Ba-Cu-O Superconductors Prepared by the "mpmg" Method

    NASA Astrophysics Data System (ADS)

    Sugawara, K.; Baar, D. J.; Murakami, M.; Kondoh, A.; Yamaguchi, K.; Shiohara, Y.; Tanaka, S.

    The electron spin resonances of both DPPH surface coatings and Y2Ba1Cu1O5 ("211" phase) non-superconducting inclusions have been used to probe the flux pinning in high critical current density Y-Ba-Cu-O bulk superconductors prepared by the "MPMG" (Melt-Powder-Melt-Growth) method. The ESR lineshapes for both the surface coatings and the 211 inclusions were observed to broaden when the MPMG samples entered the superconducting state. The excess ESR linewidth for the DPPH coatings was found to increase monotonically with decreasing temperature, as the result of increasing field gradients due to pinned flux. The ESR linewidth of the 211 inclusions had a complicated temperature dependence. This linewidth was less than that of isolated Y2Ba1Cu1O5 below 20 K, possibly due to a lower magnetic ordering temperature, mechanical stress, and/or different composition of the inclusions as compared to isolated Y2Ba1Cu1O5. Strong hysteresis in the ESR linewidths due to flux trapping was observed at low temperatures. Comparisons with the ESR linewidth of DPPH coated on the surface of the samples suggest that this flux trapping is due to strong pinning in the neighborhood of the 211 inclusions.

  7. ESR study of free radicals in mango

    NASA Astrophysics Data System (ADS)

    Kikuchi, Masahiro; Hussain, Mohammad S.; Morishita, Norio; Ukai, Mitsuko; Kobayashi, Yasuhiko; Shimoyama, Yuhei

    2010-01-01

    An electron spin resonance (ESR) spectroscopic study of radicals induced in irradiated fresh mangoes was performed. Mangoes in the fresh state were irradiated with γ-rays, lyophilized and then crushed into a powder. The ESR spectrum of the powder showed a strong main peak at g = 2.004 and a pair of peaks centered at the main peak. The main peak was detected from both flesh and skin specimens. This peak height gradually decreased during storage following irradiation. On the other hand, the side peaks showed a well-defined dose-response relationship even at 9 days post-irradiation. The side peaks therefore provide a useful means to define the irradiation of fresh mangoes.

  8. Flux properties in Bi-2212 single crystals studied by spin-probe ESR

    NASA Astrophysics Data System (ADS)

    Nishida, Akihiko; Taka, Chihiro; Yasuda, Takashi; Horai, Kazumi

    2000-07-01

    Flux properties in Bi 2Sr 2CaCu 2O 8+ x (Bi-2212) single crystals are studied by spin-probe method. ESR line widths of a very thin layer of DPPH free radical on the surface of the crystals begin to increase upon the superconducting transitions. At further low temperatures below irreversibility lines, distinct hysteresis is observed between ESR profiles for field increase and decrease. The resonance fields and intensities also indicate characteristic changes. Close correlations between ESR anomalies and vortex behaviors are discussed, comparing results of as-grown and optimally doped crystals.

  9. ESR studies of semicontinuous emulsion polymerization

    SciTech Connect

    Lau, W.; Westmoreland, D.G.

    1993-12-31

    Electron spin resonance (ESR) is used in the detection and quantification of propagating radicals during a semicontinuous emulsion polymerization. The propagating radical concentration is crucial for the determination of kinetic parameters of the emulsion polymerization process. A flow reactor was built which involves a closed-loop flow system that circulates latex from the polymerization reactor through the ESR cavity for free-radical measurements and back to the reactor. With the continuous measurement of the radical concentrations during a polymerization of methyl methacrylate (MMA), {bar n} (average number of radicals per particle) and k{sub p} (propagating rate constant), are measured throughout the entire polymerization. For the polymerization of the MMA system studied, the authors observed a gradual increased in n and decrease in k{sub p} during the run, suggesting a diffusionally controlled process and that the polymerization is not occurring homogeneously throughout the polymer particles. In the glassy pMMA matrix, radicals can be {open_quotes}trapped{close_quotes} within a minimum volume and remain unterminated.

  10. ESR studies on bleached sedimentary quartz

    NASA Astrophysics Data System (ADS)

    Walther, R.; Zilles, D.

    Some ESR signals in quartz are reported to be bleachable by sunlight and so they promise to be useful for dating sediments (Grün, 1989). The Ge signal in quartz is the only one that shows bleaching effects with UV light in short time scales (hours). Therefore we used quartz samples from the sites of Mauer ( 'Homo erectus heidelbergensis'), samples from a borehole in the Neckar valley ('Entensee', Ladenburg near Heidelberg) and samples from a pegmatite for basic studies on the Ge signal. The results show that with our standard sample preparation procedure for quartz separation (using red light as for TL samples), the natural Ge signal is not detectable, but rises clearly with gamma irradiation. Several experiments for examination of the stability and sensitivity of the Ge centre in quartz were carried out. For comparison with the behaviour of the Ge signal we measured the Al signal as well. Our experiments show that the Al signal is bleachable in long time scales (weeks). The behaviour on bleaching, irradiation and thermal annealing is very complicated, as the Al centre is a hole centre (it possibly interacts with several electron centres in the quartz and so the processes are of higher order).

  11. ESR, electrochemical and reactivity studies of antitrypanosomal palladium thiosemicarbazone complexes

    NASA Astrophysics Data System (ADS)

    Otero, Lucía; Folch, Christian; Barriga, Germán; Rigol, Carolina; Opazo, Lucia; Vieites, Marisol; Gambino, Dinorah; Cerecetto, Hugo; Norambuena, Ester; Olea-Azar, Claudio

    2008-08-01

    Cyclic voltammetry (CV) and electron spin resonance (ESR) techniques were used in the investigation of novel palladium complexes with bioactive thiosemicarbazones derived from 5-nitrofurane or 5-nitrofurylacroleine. Sixteen palladium complexes grouped in two series of the formula [PdCl 2HL] or [PdL 2] were studied. ESR spectra of the free radicals obtained by electrolytic reduction were characterized and analyzed. The ESR spectra showed two different hyperfine patterns. The stoichiometry of the complexes does not seem to affect significantly the hyperfine constants however we observed great differences between 5-nitrofurane and 5-nitrofurylacroleine derivatives. The scavenger properties of this family of compounds were lower than Trolox.

  12. Electron Spin Resonance (ESR) Studies of Returned Comet Nucleus Samples

    NASA Technical Reports Server (NTRS)

    Tsay, Fun-Dow; Kim, Soon Sam; Liang, Ranty H.

    1997-01-01

    Electron Spin Resonance (ESR) studies have been carried out on organic and inorganic free radicals generated by gamma-ray and/or UV-irradiation and trapped in ice matrices. It is suggested that the concentration of these free radicals together with their thermal stability can be used as an accurate built-in geothermometer and radiation probe for returned comet nucleus sample studies. ESR studies have also been carried out on paramagnetic (Mn(2+), Ti(3+), and Fe(3+)) and ferromagnetic (ferric oxide and metallic iron) centers known to be present in terrestrial and extraterrestrial samples. The presence or absence of these magnetic centers coupled with their characteristic ESR lineshape can be used to investigate the shock effects, quenching/cooling rate and oxidation-reduction conditions in the formation and subsequent evolution of returned comet nucleus samples.

  13. Radiostability of butylated hydroxytoluene (BHT): An ESR study

    NASA Astrophysics Data System (ADS)

    Tuner, H.; Korkmaz, M.

    2007-05-01

    In the present work, the effects of gamma radiation on solid butylated hydroxytoluene (BHT), which is used as an antioxidant, were investigated by ESR spectroscopy. While unirradiated BHT presented no ESR signal, irradiated BHT exhibited an ESR spectrum with many resonance maxima and minima spread over a magnetic field range of 12 mT and centered at about g = 2.0026. Weak satellite and central intense resonance lines, likely, originated from radical species of different stabilities and ratios were observed to be responsible from experimental ESR spectrum of gamma irradiated BHT. Studies based on the variations of the observed line intensities and spectrum area under different experimental conditions were carried out and characteristic features of the radical species responsible from experimental ESR spectrum were determined. Mesomeric radical species of different stabilities providing to BHT a G value of 0.25 were believed to be induced in gamma irradiated BHT. While species responsible from weak satellite lines were unstable, the species causing central intense lines were found to be relatively stable. BHT belongs to a class of compounds with low radiosensitivity ( G = 0.25). This feature of BHT enables the feasibility of radiosterilizations of the products containing BHT as antioxidant without very much loss from its antioxidant benefit. BHT has been shown to provide an opportunity in the estimation of applied radiation dose with a reasonable accuracy if an appropriate mathematical function is used to describe experimental dose-response data.

  14. ESR studies of the interaction of copper(II)GHK, histidine, and Ehrlich cells.

    PubMed

    Antholine, W E; Petering, D H; Pickart, L

    1989-03-01

    The tridentate complex CuGHK does not form ESR detectable adducts upon addition to either glutathione or Ehrlich ascites cells under our conditions. The absence of adducts is consistent with the poor uptake of CuGHK by cells. ESR spectra are used to characterize adduct formation between CuGHK and histidine. The CuGHK-histidine adduct is not stable in the presence of Ehrlich ascites tumor cells. It is argued that a Cu(His)2 complex is formed as a consequence of the interaction of GHK with cells. PMID:2542448

  15. Electron Spin Resonance (ESR) studies of returned comet nucleus samples

    NASA Technical Reports Server (NTRS)

    Tsay, Fun-Dow; Kim, Soon Sam; Liang, Ranty H.

    1989-01-01

    The most important objective of the Comet Nucleus Sample Returm Mission is to return samples which could reflect formation conditions and evolutionary processes in the early solar nebula. It is expected that the returned samples will consist of fine-grained silicate materials mixed with ices composed of simple molecules such as H2O, NH3, CH4 as well as organics and/or more complex compounds. Because of the exposure to ionizing radiation from cosmic-ray, gamma-ray, and solar wind protons at low temperature, free radicals are expected to be formed and trapped in the solid ice matrices. The kind of trapped radical species together with their concentration and thermal stability can be used as a dosimeter as well as a geothermometer to determine thermal and radiation histories as well as outgassing and other possible alternation effects since the nucleus material was formed. Since free radicals that are known to contain unpaired electrons are all paramagnetic in nature, they can be readily detected and characterized in their native form by the Electron Spin Resonance (ESR) method. In fact, ESR has been shown to be a non-destructive, highly sensitive tool for the detection and characterization of paramagnetic, ferromagnetic, and radiation damage centers in terrestrial and extraterrestrial geological samples. The potential use of ESR as an effective method in the study of returned comet nucleus samples, in particular, in the analysis of fine-grained solid state icy samples is discussed.

  16. Sonochemical activation of hematoporphyrin: an ESR study.

    PubMed

    Yumita, N; Nishigaki, R; Umemura, K; Morse, P D; Swartz, H M; Cain, C A; Umemura, S

    1994-05-01

    The production of 2,2,6,6-tetramethyl-4-piperidone-N-oxyl by reaction of 2,2,6,6-tetramethyl-4-piperidone (TMPone) with ultrasonically generated active species in oxygenated solutions of hematoporphyrin (Hp) was studied by electron spin resonance spectroscopy. The nitroxide production rate in air-saturated TMPone solutions in phosphate-buffered saline of pH 9.0 was significantly higher in the presence of Hp than in its absence. The enhancement of nitroxide production by Hp was significantly inhibited in the presence of sodium azide or histidine in the solution. The production rate with Hp was doubled by substitution of deuterium oxide, while the rate without Hp increased only modestly. These results suggest that a substantial amount of active oxygen can be generated by ultrasound in aqueous solutions of Hp. Since the production rate was not reduced by mannitol and no nitroxide was produced in nitrogen-saturated solutions, it appears that hydroxyl radicals do not account for a major portion of the active oxygen species which reacted with TMPone to yield a nitroxide. PMID:8183986

  17. Study on anisotropic quantum transport in graphene sheets by ESR

    NASA Astrophysics Data System (ADS)

    Yan, Liqin; Sun, Young; Huang, Jiao; Chen, Xiaolong

    Quantum transport in graphene has attracted much attention due to its excellent thermal conductivity and high room-temperature electron mobility. Using the electron spin resonance (ESR) spectrometer for studying weak localization (WL) and weak antilocalization (WAL) effects, except for having the obvious advantage of no need for electrical contacts, differs from the electric transport measurement technique also in the dominant signal from the surface of the layer not from the bulk substrate. Here we have studied an experimental anisotropic quantum transport performed on an assemblage of vertical aligned graphene sheets from 5 to 300 K by a Bruker X-band (9.3 GHz). An anisotropic quantum transport is observed between b with WL and c with WAL axes at 5 - 50 K. With increasing temperature, the transport mechanism is changed along b and c axes. We use WL theory to fit all the spectra and obtain the coherence length Lϕ, long range scattering length Llr, intervalley scattering length Li and analyze the data. Our results indicate that ESR is a robust platform to study the intrinsic physical properties of graphene.

  18. ESR study of superconducting K-doped C 60 "polymer"

    NASA Astrophysics Data System (ADS)

    Kinoshita, N.; Grigoryan, L. S.; Kinoshita, T.; Tokumoto, M.

    1997-03-01

    ESR measurements of the superconducting K-doped C 60 "polymer" were carried out, in order to clarify the difference from ordinary K-doped C 60, i.e. monomer. Observed ESR spectrum was simulated by four Lorentzian lines. The temperature dependences of the ESR linewidth, g factor and spin susceptibility are obtained for each ESR line. At room temperature the linewidth and g factor of the broadest ESR absorption line are, about 400 G and 2.01, respectively. The linewidths for other lines are 150, 53 and 16 G with the common g factor of 2.000. The linewidths of the ESR spectrum of superconducting K-doped C 60 "polymer" are found to be much broader than those of monomer sample. Similar to monomer sample, two absorption lines with weakly temperature-dependent intensity were observed, one of which disappeared (150 G width) below the super-conducting transition temperature ( Tc = 15 K).

  19. A simple double quantum coherence ESR sequence that minimizes nuclear modulations in Cu2+-ion based distance measurements

    NASA Astrophysics Data System (ADS)

    Ruthstein, Sharon; Ji, Ming; Shin, Byong-kyu; Saxena, Sunil

    2015-08-01

    Double quantum coherence (DQC) ESR is a sensitive method to measure magnetic dipolar interactions between spin labels. However, the DQC experiment on Cu2+ centers presents a challenge at X-band. The Cu2+ centers are usually coordinated to histidine residues in proteins. The electron-nuclear interaction between the Cu2+ ion and the remote nitrogen in the imidazole ring can interfere with the electron-electron dipolar interaction. Herein, we report on a modified DQC experiment that has the advantage of reduced contributions from electron-nuclear interactions, which enhances the resolution of the DQC signal to the electron-electron dipolar modulations. The modified pulse-sequence is verified on Cu2+-NO system in a polyalanine-based peptide and on a coupled Cu2+ system in a polyproline-based peptide. The modified DQC data were compared with the DEER data and good agreement was found.

  20. Metal-containing polyacrylonitriles: ESR studies and conductivity

    SciTech Connect

    Bronstein, L.M.; ERemin, V.S.; Solodovnikov, S.P.

    1995-12-01

    Metal-containing polyacrylonitriles (PAN) synthesized by the complexation of VI B group metal hexacarbonyls with PAN nitrile groups were studied during thermolysis in air at 220{degrees}C to find conditions for preparation of conductive polymeric films. It was shown that increase of W content in polymer leads to significant decrease of {gamma}{sub v} to magnitude about 10{sup -16} {Omega}/cm as compared with conductivity of thermolized initial PAN ({gamma}{sub v} = 10{sup -11} {Omega}/cm). In contrast, PAN-Cr samples heated under the same temperature-time conditions in an external field 40-50 kV/cm show the increase of conductivity: at a chromium content of 3.1 wt.% {gamma}{sub v} reaches a value of 10{sup -5} {Omega}/cm. According to ESR study, the thermolized PAN-Cr contains Cr{sub 2}O{sub 3} particles (a broad ESR signal at H=65 Oe); in so doing rough estimate of Cr{sub 2}O{sub 3} dispersity gives a value about 3 nm. Upon thermolysis of PAN-Mo in external field the enhancement of conductivity also occurs. The values of the temperature resistance factors for PAN-Cr and PAN-Mo in the temperature range 20-200{degrees}C reaches a value 1-9 x 10{sup -4} K{sup -1}.

  1. ESR, optical absorption, IR and Raman studies of xTeO{sub 2} + (70 - x)B{sub 2}O{sub 3} + 5TiO{sub 2} + 24R{sub 2}O:1CuO (x = 10, 35 and 60 mol%; R = Li, Na and K) quaternary glass system

    SciTech Connect

    Suresh, S.; Gayathri Pavani, P.; Chandra Mouli, V.

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Peak of Cu{sup 2+} is found to be maximum at around 794 nm for lithium boro tellurite glasses. Black-Right-Pointing-Pointer Variation in g{sub ||} and A{sub ||} values is due to change in environment of Cu{sup 2+} ion due to the structural change in the glass. Black-Right-Pointing-Pointer BO{sub 3}-BO{sub 4}{sup -} ring structure is interconnected by TeO{sub 3}{sup -} and TeO{sub 4}{sup -} groups, where the BO{sub 4}{sup -} groups are neighbors of TeO{sub 3}{sup -}groups. Black-Right-Pointing-Pointer The structure comprising, isolate a BO{sub 3}{sup -}, B{sub 2}O{sub 5}, BO{sub 4}{sup -}, and metaborates, which enables glass forming for Borate rich glasses. Black-Right-Pointing-Pointer Distorted TeO{sub 4/2} network with BO{sub 3}{sup -}-BO{sub 4}{sup -} ring structure and TeO{sub 3}{sup -} group is enables glass forming for tellurite rich glasses. -- Abstract: xTeO{sub 2} + (70 - x)B{sub 2}O{sub 3} + 5TiO{sub 2} + 24R{sub 2}O:1CuO (x = 10, 35 and 60; R = Li, Na and K) glass system were studied by spectroscopic techniques such as ESR, optical absorption, Raman and IR. From ESR spectra, the spin Hamiltonian parameter values indicate that the ground state of Cu{sup 2+} is d{sub x{sup 2}-y{sup 2}} and the site symmetry around the Cu{sup 2+} ion is tetragonally distorted octahedral coordination. Bonding parameters calculated from optical absorption and ESR data are found to change with alkali oxide and TeO{sub 2} content. Bonding parameters indicate a slight covalency for the in-plane {sigma} bonding as compared to in-plane and out-of-plane {pi} bonds. Both Raman and IR results show that glass network consists of TeO{sub 3}, TeO{sub 4}, BO{sub 3}, BO{sub 4} and RiO{sub 4} group as basic structural groups. BO{sub 3}-BO{sub 4}{sup -} ring structure interconnected by TeO{sub 3}{sup -} and TeO{sub 4}{sup -} groups, where the BO{sub 4}{sup -} groups are neighbors of the TeO{sub 3}{sup -} groups. BO{sub 3} {yields} BO{sub 4

  2. Diffusion studies on permeable nitroxyl spin probes through bilayer lipid membranes: A low frequency ESR study

    SciTech Connect

    Meenakumari, V.; Benial, A. Milton Franklin; Utsumi, Hideo; Ichikawa, Kazuhiro; Yamada, Ken-ichi; Hyodo, Fuminori; Jawahar, A.

    2015-06-24

    Electron spin resonance (ESR) studies were carried out for permeable 2mM {sup 14}N-labeled deutrated 3 Methoxy carbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) in pure water and 1mM, 2mM, 3mM, 4mM concentration of 14N-labeled deutrated MC-PROXYL in 400mM concentration of liposomal solution by using a 300 MHz ESR spectrometer. The ESR parameters such as linewidth, hyperfine coupling constant, g-factor, partition parameter and permeability were reported for these samples. The line broadening was observed for the nitroxyl spin probe in the liposomal solution. The line broadening indicates that the high viscous nature of the liposomal solution. The partition parameter and permeability values indicate the maximum diffusion of nitroxyl spin probes in the bilayer lipid membranes at 2 mM concentration of nitroxyl radical. This study illustrates that ESR can be used to differentiate between the intra and extra- membrane water by loading the liposome vesicles with a lipid-permeable nitroxyl spin probe. From the ESR results, the spin probe concentration was optimized as 2mM in liposomal solution for ESR phantom studies/imaging, invivo and invitro experiments.

  3. Diffusion studies on permeable nitroxyl spin probes through bilayer lipid membranes: A low frequency ESR study

    NASA Astrophysics Data System (ADS)

    Meenakumari, V.; Utsumi, Hideo; Ichikawa, Kazuhiro; Yamada, Ken-ichi; Hyodo, Fuminori; Jawahar, A.; Benial, A. Milton Franklin

    2015-06-01

    Electron spin resonance (ESR) studies were carried out for permeable 2mM 14N-labeled deutrated 3 Methoxy carbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) in pure water and 1mM, 2mM, 3mM, 4mM concentration of 14N-labeled deutrated MC-PROXYL in 400mM concentration of liposomal solution by using a 300 MHz ESR spectrometer. The ESR parameters such as linewidth, hyperfine coupling constant, g-factor, partition parameter and permeability were reported for these samples. The line broadening was observed for the nitroxyl spin probe in the liposomal solution. The line broadening indicates that the high viscous nature of the liposomal solution. The partition parameter and permeability values indicate the maximum diffusion of nitroxyl spin probes in the bilayer lipid membranes at 2 mM concentration of nitroxyl radical. This study illustrates that ESR can be used to differentiate between the intra and extra- membrane water by loading the liposome vesicles with a lipid-permeable nitroxyl spin probe. From the ESR results, the spin probe concentration was optimized as 2mM in liposomal solution for ESR phantom studies/imaging, invivo and invitro experiments.

  4. ESR study of AuEr dilute alloys

    NASA Astrophysics Data System (ADS)

    Dokter, H. D.; Davidov, D.; Hoekstra, F. R.; Nieuwenhuys, G. J.

    1981-06-01

    ESR linewidth and signal intensity measurements of AuEr (0.2%, 1%, 3%) dilute alloys have been carried out as a function of temperature in order to resolve previous discrepancies regarding the crystal field splitting. The data analysis indicates a splitting of (16 ± 4) K between the Γ 7 ground state and the Γ (1)8 first excited state. No evidence for an additional broadening mechanism associated with Er-Er exchange interactions was observed.

  5. ESR Study on Irradiated Ascorbic Acid Single Crystal

    SciTech Connect

    Tuner, H.; Korkmaz, M.

    2007-04-23

    Food irradiation is a 'cold' process for preserving food and has been established as a safe and effective method of food processing and preservation after more than five decades of research and development. The small temperature increase, absence of residue and effectiveness of treatment of pre-packed food are the main advantages. In food industry, ascorbic acid and its derivatives are frequently used as antioxidant agents. However, irradiation is expected to produces changes in the molecules of food components and of course in the molecules of the agents added as preservation agents such as ascorbic acid. These changes in the molecular structures could cause decreases in the antioxidant actions of these agents. Therefore, the radiation resistance of these agents must be known to determine the amount of radiation dose to be delivered. Electron spin resonance (ESR) is one of the leading methods for identification of intermediates produced after irradiation. ESR spectrum of irradiated solid powder of ascorbic acid is fairly complex and determinations of involved radical species are difficult. In the present work, single crystals of ascorbic acid irradiated by gamma radiation are used to determine molecular structures of radiation induced radicalic species and four radicalic species related in pair with P21 crystal symmetry are found to be responsible from experimental ESR spectrum of gamma irradiated single crystal of ascorbic acid.

  6. An ESR study of radiation induced radicals in glucose polymers

    NASA Astrophysics Data System (ADS)

    Kameya, Hiromi; Ukai, Mitsuko; Shimoyama, Yuhei

    2013-03-01

    Using electron spin resonance (ESR) spectroscopy with both experimental and theoretical approaches, we revealed the γ-radiation induced radicals in two glucose polymers, cellulose and starch. Before irradiation, ESR signals are silent in both the glucose polymers. After irradiation, a singlet signal at g=2.0 appeared in both the glucose polymers. The twin peaks were invisible in the starch sample. We identified the twin peaks to be a part of triplet signal and analyzed the molecular structure of the cellulose radical. Through theoretical simulations, we revealed, for the first time, that the triplet signal was due to hyperfine interactions of unpaired electron with two protons in the cellulose radical. The third peak within the triplet is overlapped by the free radical at g=2.0. We further found that the cellulose radical does not remain at the rigid limit or the static state, but undergoes axial rotations around C-C and C-H bonds. We concluded that the triplet ESR signal reflects the cellulose radical.

  7. Radical cations of sulfides and disulfides: An ESR study

    SciTech Connect

    Bonazzola, L.; Michaut, J.P.; Roncin, J.

    1985-09-15

    Exposure of dilute solutions of dimethylsulfide, methanethiol, tetrahydrothiophene, terbutyl and diterbutyl-sulfides, dimethyl-disulfide, and diterbutyldisulfide, in freon at 77 K to /sup 60/Co ..gamma.. rays gave the corresponding cations. From the reported ESR spectra, g tensors were obtained. It was found that both sulfide and disulfide cations exhibit the same g tensor: (g/sub max/ = 2.034 +- 0.002, g/sub int/ = 2.017 +- 0.001, g/sub min/ = 2.001 +- 0.005). From this result it has been shown that the disulfide cation is planar. This finding was supported by fully optimized geometry ab initio calculations.

  8. ESR, SIMS and TEMF of an Y-Ba-Cu-O superconductor

    NASA Technical Reports Server (NTRS)

    Kirschner, I.; Giber, J.; Halasz, I.

    1995-01-01

    Superconducting transition comes into being between 92 K and 82 K in the samples having a Meissner's state value of 68 vol. percent. The main material content has an orthorhombic unit cell of Y1Ba2Cu408 accompanied by low quantity CuO and a sporadic phase. A proof of anisotropic superconductivity, an unusually high Cu ion concentration and a temperature dependent transition of charge carriers have been observed.

  9. ESR studies on hot-wire amorphous silicon

    SciTech Connect

    Unold, T.; Mahan, A.H.

    1997-07-01

    The authors measure a series of hot-wire (HW) amorphous silicon films grown with hydrogen contents C{sub H} varying between 0.5--17 at.%. From constant photocurrent method (CPM) measurements and the steady-state photocarrier grating method (SSPG) they find good agreement with previous measurements on similar hot-wire films. Electron spin resonance measurements on the same samples, however, yield significantly higher spin densities than expected. A thickness series indicates a highly defective layer close to the substrate interface. They propose that this defective layer may be due to excessive out diffusion of hydrogen during growth at high temperatures, as seen by secondary ion mass spectroscopy. ESR measurements on light-degraded samples indicate an improved stability of samples with C{sub H} < 9 at.%.

  10. Mechanism of Cr(VI) adsorption by coir pith studied by ESR and adsorption kinetic.

    PubMed

    Suksabye, Parinda; Nakajima, Akira; Thiravetyan, Paitip; Baba, Yoshinari; Nakbanpote, Woranan

    2009-01-30

    The oxidation state of chromium in coir pith after Cr(VI) adsorption from aqueous solution was investigated using electron spin resonance (ESR). To elucidate the mechanism of chromium adsorption on coir pith, the adsorption studies of Cr(VI) onto lignin, alpha-cellulose and holocellulose extracted from coir pith were also studied. ESR signals of Cr(V) and Cr(III) were observed in coir pith adsorbed Cr(VI) at solution pH 2, while ESR spectra of lignin extracted from coir pith revealed only the Cr(III) signal. In addition, ESR signal of Cr(V) was observed in alpha-cellulose and holocellulose extracted from coir pith adsorbed Cr(VI). These results confirmed that lignin in coir pith reduced Cr(VI) to Cr(III) while alpha-cellulose and holocellulose extracted from coir pith reduced Cr(VI) to Cr(V). The Cr(V) signal exhibited in ESR of alpha-cellulose and holocellulose might be bound with glucose in cellulose part of coir pith. In addition, xylose which is main in pentosan part of coir pith, indicated that it is involved in form complex with Cr(V) on coir pith. The adsorption kinetic of Cr(VI) from aqueous solution on coir pith was also investigated and described well with pseudo second order model. ESR and desorption experiments confirmed that Cr(VI), Cr(V) and Cr(III), exist in coir pith after Cr(VI) adsorption. The desorption data indicated that the percentage of Cr(VI), Cr(V) and Cr(III) in coir pith were 15.63%, 12.89% and 71.48%, respectively. PMID:18513862

  11. In vivo copper-mediated free radical production: an ESR spin-trapping study

    NASA Astrophysics Data System (ADS)

    Kadiiska, Maria B.; Mason, Ronald P.

    2002-04-01

    Copper has been suggested to facilitate oxidative tissue injury through a free radical-mediated pathway analogous to the Fenton reaction. By applying the electron spin resonance (ESR) spin-trapping technique, evidence for hydroxyl radical formation in vivo was obtained in rats treated simultaneously with copper and ascorbic acid or paraquat. A secondary radical spin-trapping technique was used in which the hydroxyl radical formed the methyl radical upon reaction with dimethylsulfoxide. The methyl radical was then detected by ESR spectroscopy as its adduct with the spin trap phenyl- N- t-butyl- nitrone (PBN). In contrast, lipid derived radical was detected in vivo in copper-challenged, vitamin E and selenium-deficient rats. These findings support the proposal that dietary selenium and vitamin E can protect against lipid peroxidation and copper toxicity. Since copper excreted into the bile from treated animals is expected to be maintained in the Cu(I) state (by ascorbic acid or glutathione), a chelating agent that would redox-stablilize it in the Cu(I) state was used to prevent ex vivo redox chemistry. Bile samples were collected directly into solutions of bathocuproinedisulfonic acid, a Cu(I)-stabilizing agent, and 2,2'-dipyridyl, a Fe(II)-stabilizing agent. If these precautions were not taken, radical adducts generated ex vivo could be mistaken for radical adducts produced in vivo and excreted into the bile.

  12. Solid-state NMR and ESR studies of activated carbons produced from pecan shells

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Activated carbon from pecan shells has shown promise as an adsorbent in water treatment and sugar refining. However, the chemistry of the material is complex and not fully understood. We report here the application of solid state NMR and ESR to study the chemical structure, mobility, and pore volu...

  13. ESR studies of surface adsorption and catalysis under ultra-high vacuum conditions. Progress report, March 1, 1980-February 29, 1981

    SciTech Connect

    Freed, J.H.

    1980-11-01

    This project is directed to developing ESR for the study of surface adsorption and catalysis on clean well-characterized metallic and oxide surfaces under ultra-high vacuum (UHV) conditions and to compare the results with real surfaces, which are important in actual catalysis. Results with ESR-UHV system on the NO/sub 2//Cu system showed that only in the presence of H/sub 2/O can the surface process(es) proceed that lead to stable Cu/sup 2 +/ complexes which are observable by ESR. By monitoring the CREMSEE (cyclotron-resonance from microwave-induced secondary electron emissions) threshold, definite evidence for the oxidation of the Cu surface by the clean NO/sub 2/ has been obtained. In real systems, as opposed to the clean surfaces prepared under UHV conditions, small amounts of H/sub 2/O are usually present. The UHV studies permitted a demonstration of the reactivity requirements. Detailed studies of the oxidation process of NO/sub 2/ on Cu have been performed. A newer ESR-UHV system with better expected performance has been built. An extensive study of motional dynamics of free radicals on supported surfaces has been completed. These include the O/sub 2//sup -/ radical absorbed on Ti supported on crushed vycor and NO/sub 2/ adsorbed on crushed vycor. The O/sub 2//sup -/ is found to exhibit planar rotation about an axis perpendicular to the internuclear axis of the O/sub 2//sup -/ and parallel to the normal to the plane. The higher temperature motion may be fit with a small activation energy of 0.5Kcal/mole, while the lower temperature motion shows anomalies. The NO/sub 2/ exhibits planar-rotation at the lower temperature, but above 77/sup 0/K it becomes more nearly isotropic presumably due to translational diffusion. Preliminary experiments imply that addition of acetylene increases the rate of rotational motion of the O/sub 2//sup -/. Preliminary studies leading to time-resolved UHV-ESR experiments of photo-induced catalysis have been performed with the new

  14. Transport and recombination channels in undoped microcrystalline silicon studied by ESR and EDMR

    SciTech Connect

    Will, D.; Lerner, C.; Fuhs, W.; Lips, K.

    1997-07-01

    The authors present a detailed study of ESR and spin-dependent transport (EDMR) on {micro}c-Si. They identify to different types of defects at g = 2.0055({+-}3) and g = 2.0044({+-}5) and study their influence on transport and recombination by stepwise annealing the samples. They find that transport is not controlled by defects if N{sub D} < 10{sup 18} cm{sup {minus}3}. For N{sub D} > 10{sup 18} cm{sup {minus}3} a dramatic decrease of the conductivity is found and they identify a hopping contribution in transport. To explain their ESR and EDMR results they propose a simple model where most defects are distributed at the surface of the columns and transport is along percolation paths. They also observe minor metastable changes of the defect density which are assigned to adsorption of atmospheric oxygen.

  15. An FTIR and ESR study of iron doped calcium borophosphate glass-ceramics

    NASA Astrophysics Data System (ADS)

    Karabulut, M.; Popa, A.; Borodi, G.; Stefan, R.

    2015-12-01

    A series of glasses in the xFe2O3-(100-x) [42B2O3-24CaO-34P2O5] system has been prepared for x = 0-10. Structure of as casted glasses and their heat treated counterparts have been studied by X-ray diffraction, infrared and electron spin resonance spectroscopies. Amorphous nature of all of the compositions studied is confirmed by the XRPD spectra. After the heat treatment, besides the main BPO4 phase, CaBPO5 and Ca(PO3) crystalline phases were identified in the iron free glass while B0.57Fe0.43PO4 phase was also observed in the XRD pattern of iron containing samples. FTIR spectra indicate changes in the glass network upon iron addition. X-band ESR spectra exhibits resonance signals at g ∼ 2.0 and g ∼ 4.3 for all analyzed samples. A supplementary line centered at g ∼ 6 appears after the thermal treatment. The nature of ESR absorption signals and influence of iron content on the evolution of ESR parameters are discussed.

  16. ESR studies of surface adsorption and catalysis under ultra-high vacuum conditions. Progress report, March 1, 1982-February 28, 1983

    SciTech Connect

    Freed, J. H.

    1982-09-01

    A study was conducted of the new phenomenon of surface-suppressed ESR (SSESR), in which stable paramagnetic radicals adsorbed on clean Ag or Cu surfaces have their ESR signal suppressed until several layers of molecules insulate subsequent layers from the metal surface. This study combined UHV-ESR, CREMSEE, and thermal desorption. A tentative model based upon transmission of the effects of the surface conduction band of the metal by the weak exchange forces between the paramagnetic species was suggested. Experiments on a model system by means of Laser Time Resolved ESE spectroscopy were performed. A photo-induced transient electron was produced from Rb ions in nonpolar medium. The spin relaxation of the transient electron was studied vs temperature and alkali metal concentration. The transient electron is initially spin-polarized, and the degree of spin-polarization is affected by the wavelength. Such an effect would be expected from a long-lived geminate radical-pair mechanism (Rb/sup +/ + e/sup -/) causing the spin-polarization, with the initial separation distance affected by the energy of the photon absorbed. An extended Hueckel MO analysis of our previous O/sub 2//sup -//Ti-vycor study was completed; a new and improved photo-CREMSEE apparatus was completed and utilized; motional dynamics of NO/sub 2/ on zeolites was analyzed; and work was conducted on a photo-induced source of H atoms for Laser Time Resolved ESE experiments were carried out.

  17. Association study of the estrogen receptor gene ESR1 with post-partum depression – a pilot study

    PubMed Central

    Pinsonneault, Julia K.; Sullivan, Danielle; Sadee, Wolfgang; Soares, Claudio N.; Hampson, Elizabeth; Steiner, Meir

    2013-01-01

    Perinatal mood disorders, such as postpartum depression (PPD) are costly for society, with potentially serious consequences for mother and child. While multiple genes appear to play a role in PPD susceptibility, the contributions of specific genetic variations remain unclear. Previously implicated as a candidate gene, the estrogen receptor alpha gene (ESR1) is a key player in mediating hormonal differences during pregnancy and the postpartum period. This study addresses genetic factors in perinatal mood disorders, testing 9 polymorphisms in ESR1. 257 postpartum women were screened for mood disorders, including 52 women with PPD and 32 without any symptoms of mood disorders. We detected a significant association for the upstream TA microsatellite repeat with the Edinburgh Postnatal Depression Scale (p=0.007). The same variant was also associated with the occurrence of PPD. Separately, 11 candidate functional polymorphisms in 7 additional genes were genotyped to investigate gene-gene interaction with the ESR1 TA repeat, identifying a potential interaction with the serotonin transporter. Our results support a role for ESR1 in the etiology of PPD, possibly through the modulation of serotonin signaling. Our findings for ESR1 could have broad implications for other disorders and therapies that involve estrogens. PMID:23917948

  18. Synthesis and ESR studies of 2'-deoxyuridines tethered with alkynyl, rod-like linkages#

    PubMed Central

    Sniady, Adam; Sevilla, Michael D.; Meneni, Srinivasarao; Lis, Tadeusz; Szafert, Slawomir; Khanduri, Deepthi; Finke, John M.; Dembinski, Roman

    2015-01-01

    Sonogashira coupling of diacetyl 5-ethynyl-2'-deoxyuridine with diacetyl 5-iodo-2'-deoxyuridine gave the acylated ethynediyl-linked 2'-deoxyuridine dimer (3b) (63%) that was deprotected with ammonia/methanol to ethynediyl-linked 2'-deoxyuridines (3a) (79%). Reaction of 5-ethynyl-2'-deoxyuridine (1a) with 5-iodo-2'-deoxyuridine gave the furopyrimidine linked to 2'-deoxyuridine (78%). Catalytic oxidative coupling of 1a (O2, CuI, Pd/C, DMF) gave the butadiynediyl-linked 2'-deoxyuridines (4) (84%). Double Sonogashira coupling of 5-iodo-2'-deoxyuridine with 1,4-bis(ethynyl)benzene gave 1,4-phenylenediethyne-bridged 5-ethynyl-2'-deoxyuridines (5, 83%). Cu-catalyzed cycloisomerization of dimers 4 and 5 gave their furopyrimidine derivatives. One electron addition to 1a, 3a and 4 gave the anion radical whose ESR spectra showed the unpaired electron largely localized at C6 of one uracil ring (17 G doublet) at 77 K. For the ethynediyl- and butadiynyl-linked uridines 3a and 4 the ESR spectra of their one electron oxidized species at 77 K showed that the unpaired electron is delocalized over both rings. Thus structures 3a and 4 provide an efficient electronic link for hole conduction between the uracil rings. However, for the excess electron, an activation barrier prevents coupling to both rings. These dimeric structures could provide a gate that could separate hole transfer from electron transport between strands in DNA systems. In the crystal structure of acylated dimer 3b the bases were found in the anti position to each other across the ethynyl link. Similar anti conformation was preserved in the derived furopyrimidine–deoxyuridine dinucleoside. PMID:19609983

  19. Spectral, magnetic, thermal, molecular modelling, ESR studies and antimicrobial activity of ( E )-3-(2-(2-hydroxybenzylidene) hydrazinyl)-3-oxo- n (thiazole-2-yl)propanamide complexes

    NASA Astrophysics Data System (ADS)

    Zaky, R. R.; Yousef, T. A.

    2011-09-01

    ( E)-3-(2-(2-hydroxybenzylidene)hydrazinyl)-3-oxo- n(thiazole-2-yl) propane-mide (H 2L) has been prepared and its structure confirmed by elemental analysis, IR and 1HNMR spectroscopy. It has been used to produce diverse complexes with Ni(II), Co(II) and Cu(II) ions. The complexes obtained have been investigated by thermal analysis, spectral studies (IR, UV-visible, ESR), and magnetic measurements. IR spectra suggest that the H 2L acts as a bidentate ligand coordinating via (C dbnd N) 1 and (OH) phenolic or deprotonated enolized carbonyl oxygen ( dbnd C sbnd O sbnd ) 1. The electronic spectra of the complexes and their magnetic moments provide information about geometries. The room temperature solid state ESR spectra of the Cu(II) complexes show d x2-y2 as a ground state, suggesting tetragonally distorted octahedral or square-planar geometries around Cu(II) centre. The molar conductance measurements proved that the complexes are non-electrolytes. The bond length, bond angle, HOMO, LUMO, dipole moment and charges on the atoms have been calculated to confirm the geometry of the ligand and the investigated complexes. Also, thermal properties and decomposition kinetics of all compounds are investigated. The interpretation, mathematical analysis and evaluation of kinetic parameters ( Ea, A, Δ H, Δ S and Δ G) of all thermal decomposition stages have been evaluated using Coats-Redfern and Horowitz-Metzger methods. Finally, the antimicrobial activity has been tested.

  20. A study of the radiation chemistry of poly(chlorotrifluoroethylene) by ESR spectroscopy

    NASA Astrophysics Data System (ADS)

    Hill, David J. T.; Thurecht, Kristofer J.; Whittaker, Andrew K.

    2003-12-01

    The ESR spectra of poly(chlorotrifluoroethylene) were recorded following γ-radiolysis under vacuum at room temperature and 77 K. The very broad spectrum at 77 K revealed little fine structure with which to identity the radicals formed upon irradiation, but subsequent photobleaching and annealing studies, together with radiolytic studies at higher temperatures, afforded scope for making radical assignments. Both main-chain radicals and a range of chain-end radicals have been identified. The G-values for radical formation were 1.55, 0.36 and 0.32 at 77 K, 273 K and room temperature, respectively.

  1. Inter-comparison study between human and cow teeth enamel for low dose measurement using ESR

    NASA Astrophysics Data System (ADS)

    Hassan, G. M.; Aboelezz, E.; El-Khodary, A.; Eissa, H. M.

    2010-07-01

    Human and cow teeth enamel samples were separated and irradiated with γ-ray to study radiation-induced radicals as dosimetric material with electron spin resonance (ESR). The enamel spectrum is characterized by two main g-factors g|| = 1.9976 and g⊥ = 2.0019. The dosimetric signal for enamel at g = 2.0019 is ascribed to CO2- radicals. The dose response was studied in the range from 200 mGy to 2 Gy. Power dependence, energy dependence and thermal stability had been studied also to determine the optimum conditions for ESR measurements and stability of the signal at room temperature as well. Radical formation efficiency ( G-value) of 0.44 ± 0.09 and 0.65 ± 0.13 was obtained for human enamel and cow enamel, respectively. The life time for human enamel and cow enamel were estimated from Arrhenius plot to be 1.1 × 10 7 years and 7 × 10 6 years, respectively. The activation energy for human enamel and cow enamel were also calculated from Arrhenius plot to be 1.23 eV and 1.15 eV, respectively. The dose conversion factors for enamel in water and air were calculated to be 0.901 Dwater and 0.998 Dair. The combined and expanded uncertainties accompanying these measurements are ±5.79% and ±11.58%, respectively.

  2. ESR studies of some. gamma. -irradiated organic crystals. [N-tert-butylacrylamide, propionamide

    SciTech Connect

    Kilic, S.; Baysal, B.M.

    1981-12-01

    Acrylamide, N-tert-butylacrylamide, and propionamide crystals were irradiated at -196/sup 0/C and the structures of radicals studied by ESR spectroscopy at various temperatures. The ..gamma..-irradiated acrylamide crystals show a five-line spectrum which is similar in shape to the signal obtained from the ..gamma..-irradiated propionamide crystals. Two types of radicals are produced in irradiated acrylamide and propionamide crystals at -196/sup 0/C. When the irradiated samples are kept at -78/sup 0/C the spectrum of propionamide remains the same, except in intensity. In contrast to this, the acrylamide spectrum changes to a triplet because of dimerization. Upon warming the irradiated acrylamide sample to between -50 and -30/sup 0/C, some small new peaks become apparent on either side of the triplet. These new peaks disappear above -20/sup 0/C and the spectrum changes to a triplet because of polymerization. To observe the changes in the ESR spectra of ..gamma..-irradiated N-tert-butylacrylamide we kept the sample at various temperatures from -196 to 100/sup 0/C. From -196/sup 0/C to about room temperature the spectrum is a quintet. At and above 35/sup 0/C, the spectrum changes to a triplet with shoulders on either side of the main peaks. With further warming above 80/sup 0/C the spectrum changes to a broad triplet.

  3. ESR and ENDOR study of the guanine cation: Secondary product in 5'-dGMP

    SciTech Connect

    Hole, E.O.; Nelson, W.H.; Close, D.M.; Sagstuen, E.

    1987-05-01

    Previous ESR studies of x-irradiated single crystals of 2'-deoxyguanosine-5'-monophosphate have indicated the presence of a radical thought to be formed by deprotonation of a primary base cation at N1. In this communication are reported some results of detailed ESR and ENDOR experiments at 10 K conflicting with the above results. One of the radicals detected exhibited two ..cap alpha..-proton type couplings. The data analysis shows that one coupling is due to the exchangeable proton of the extra-annular NH/sub 2/ group, while the other is due to the proton bonded at C8. The experimental spin densities were rho(N10) = 0.33, and rho(C8) = 0.18. The results agree reasonably well with the INDO calculated spin density distribution of a radical formed by deprotonation at N10 of a primary cation radical. The radical is stable on warming to about 200 K where it anneals rapidly.

  4. Gd{sub 3+}-ESR and magnetic susceptibility of GdCu{sub 4}Al{sub 8} and GdMn{sub 4}Al{sub 8}

    SciTech Connect

    Coldea, R.; Coldea, M.; Pop, I.

    1994-03-01

    Gd ESR of GdCu{sub 4}Al{sub 8} and GdMn{sub 4}Al{sub 8} and magnetic susceptibility of GdCu{sub 4}Al{sub 8}, GdMn{sub 4}Al{sub 8}, and YMn{sub 4}Al{sub 8} were measured in the temperature range of 290K--460K and 90K--1050K, respectively. The occurrence of the Mn moment in YMn{sub 4}Al{sub 8} and GdMn{sub 4}Al{sub 8} is strongly correlated with the critical value of d{approx}2.6{angstrom} of the Mn-Mn distance below which the Mn moment is not stable. The experimental data for GdMn{sub 4}Al{sub 8}, compared with the data for the isostructural compounds GdCu{sub 4}Al{sub 8} and YMn{sub 4}Al{sub 8}, show that near the critical value of d, the existence of Mn moment depends not only on the value of d, but also on the local magnetic surroundings. It has been revealed that the magnetic character of Mn moment in YMn{sub 4}Al{sub 8} and GdMn{sub 4}Al{sub 8} changes from an itinerant electron type to a local-moment type with increasing temperature.

  5. The chemistry of Li/SOCl2 cells - An ESR study of carbon electrodes

    NASA Technical Reports Server (NTRS)

    Kim, S. S.; Carter, B. J.; Tsay, F. D.

    1985-01-01

    Carbon electrodes from Li/SOCl2 cells were studied by electron spin resonance after various stages of discharge. Different behavior was observed in the temperature-dependent part of the ESR linewidth, defined as 'intrinsic linewidth', Delta H(int), when two different electrolytes were used. With one electrolyte, 1.5M LiAlCl4/SoCl2, the Delta H(int) value stayed constant or slightly decreased whereas with another electrolyte, 1.0M LiAlCl4/14 percent BrClin SOCl2, the value increased as discharge progressed. The carbon electrodes are modified differently during discharge with these two electrolytes, and it is speculated that this may be due to changes in the carbon matrix functional groups. This difference in the carbon electrodes may explain the claimed differences in safety performance of the cells.

  6. ESR study of 2-substituted 2-adamantyl radicals. Configuration and long-range hyperfine interaction

    SciTech Connect

    Kira, Mitsuo; Akiyama, Mieko; Ichinose, Michiko; Sakurai, Hideki )

    1989-10-11

    Structure and long-range hyperfine interaction in 2-adamantyl, 5,7-dimethyl-2-adamantyl, and the various 2-substituted radicals (substituent = CH{sub 3}, CH{sub 2}SiMe{sub 3}, OSiMe{sub 3}, SSiMe{sub 3}, CH{sub 2}GeMe{sub 3}, etc.) were studied by ESR. The origin of the long-range hyperfine interaction is discussed on the basis of the comparison between experimental and theoretical hfs values. The analyses of hfs values for persistent 2-bis(trimethylsilyl)methyl-2-adamantyl radical and the 5,7-dimethyl derivative were made by the assistance of the ENDOR spectrum.

  7. Reaction of vanadate with aquatic humic substances: An ESR and {sup 51}V NMR study

    SciTech Connect

    Lu, Xi.; Johnson, W.D.; Hook, J.

    1998-08-01

    Electron spin resonance (ESR) spectroscopy and {sup 51}V nuclear magnetic resonance (NMR) spectroscopy have been used to study the interaction of vanadate with aqueous solutions of humic substances (HS) at different pH values and at different concentrations. Under acidic pH conditions, ESR spectra show that humic substances reduce vanadium(V) to vanadium(IV) without further reduction to vanadium(III). The reduced vanadium(IV) ion is bound to oxygen donor atoms, probably at carboxylic acid sites in the humic substances. {sup 51}V NMR spectra show that the VO{sub 2}{sup +} cation is immediately reduced and that the decavanadate cation decomposes to the VO{sub 2}{sup +} cation prior to reduction. The overall rate of reduction depends on both concentration and pH. There is no reduction above pH 6, which suggests that the standard reduction potential of humic substances is about +0.65 V. Near pH 7, vanadate is stabilized by binding to humic substances. As the concentration of humic substances increases, the total vanadium NMR signal intensity decreases. This is due to the quadrupolar nature of the {sup 51}V nucleus that, when bound to humic substances, is invisible in NMR measurements. Quantitative models applied to intensity changes show that the vanadate monomer forms HS0V(V) complexes. The formation equilibrium constant is estimated to be 108 M{sup {minus}1}. At pH above 9, NMR signals appear at {minus}623.6 and at {minus}763.2 ppm when humic substances are added to vanadate solution. The intensities of the signals increase with increasing pH and with increasing concentration of humic substances. These signals appear to be associated with peroxyvanadate anions, which are not bound to humic substances.

  8. Electron Spin Resonance (ESR) Detection of Broken Time-Reversal Symmetry (BTRS) at Surfaces of YBa_2Cu_3O_7-x (YBCO) Thin Films

    NASA Astrophysics Data System (ADS)

    Pugel, D. E.

    2001-03-01

    High-Tc cuprate surfaces that break the reflection symmetry of the d-wave order parameter support bound excitations at the Fermi energy. The low-temperature (T ~0.1T_c)behavior of these bound excitations, measured as changes in the density of states, has been interpreted as a transition into a BTRS state(M. Covington et al)., Phys. Rev. Lett. 79, 277 (1997)(R. Krupke & G. Deutscher, Phys. Rev. Lett. 83, 4634 (1999).)(L. H. Greene et al)., Physica B, 280, 159 (2000).. A definitive determination of surface BTRS requires a direct measurement of a spontaneous magnetic field. We adapt traditional X-band ( ~9GHz) ESR to directly search for BTRS at surfaces of optimally-doped,oriented YBCO thin films. This technique allows for spatially localized (<50nm), time-resolved (10-11s) measurements of surface magnetic fields. Organic spin probe crystallites, reduced to nanometer-scale diameters, are applied to (110),(103),(001) YBCO, non-superconducting cuprate isostructure (110) PrBa_2Cu_3O_7, and (100),(110) SrTiO3 surfaces. The resonance response of different spin probes on these surfaces is measured as a function of temperature and applied magnetic field direction. Temperature dependence of ESR spectra for these coated surfaces shows an additional magnetic field source appearing below ~10K for only those YBCO surfaces which break reflection symmetry. The transition is independent of applied field direction, indicating an additional field source that is spontaneous in origin. Results indicate a domain structure whose net magnetization points along [001](D. E. Pugel, Y.-M. Xia, M. B. Salamon, & L. H. Greene, Physica C 341-348, 2003 (2000))(D. E. Pugel, M. B. Salamon, M. B. Weissman, & L. H. Greene, Preprint (2000).).

  9. ESR studies of spin-labeled membranes aligned by isopotential spin-dry ultracentrifugation: lipid-protein interactions.

    PubMed Central

    Ge, M; Budil, D E; Freed, J H

    1994-01-01

    Electron spin resonance (ESR) studies have been performed on spin-labeled model membranes aligned using the isopotential spin-dry ultracentrifugation (ISDU) method of Clark and Rothschild. This method relies on sedimentation of the membrane fragments onto a gravitational isopotential surface with simultaneous evaporation of the solvent in a vacuum ultracentrifuge to promote alignment. The degree of alignment obtainable using ISDU, as monitored by ESR measurements of molecular ordering for both lipid (16-PC) and cholestane spin labels (CSL), in dipalmitoylphosphatidylcholine (DPPC) model membranes compares favorably with that obtainable by pressure-annealing. The much gentler conditions under which membranes may be aligned by ISDU greatly extends the range of macroscopically aligned membrane samples that may be investigated by ESR. We report the first ESR study of an integral membrane protein, bacteriorhodopsin (BR) in well-aligned multilayers. We have also examined ISDU-aligned DPPC multilayers incorporating a short peptide gramicidin A' (GA), with higher water content than previously studied. 0.24 mol% BR/DPPC membranes with CSL probe show two distinct components, primarily in the gel phase, which can be attributed to bulk and boundary regions of the bilayer. The boundary regions show sharply decreased molecular ordering and spectral effects comparable to those observed from 2 mol% GA/DPPC membranes. The boundary regions for both BR and GA also exhibit increased fluidity as monitored by the rotational diffusion rates. The high water content of the GA/DPPC membranes reduces the disordering effect as evidenced by the reduced populations of the disordered components. The ESR spectra obtained slightly below the main phase transition of DPPC from both the peptide- and protein-containing membranes reveals a new component with increased ordering of the lipids associated with the peptide or protein. This increase coincides with a broad endothermic peak in the DSC

  10. Magnetic and ESR studies in a Quasi-two-dimensional Triangular magnet Ba3MnNb2O9

    NASA Astrophysics Data System (ADS)

    Tian, Zhaoming; Guo, Qian; Ouyang, Zhongwen; Du, Guihuan; Tong, Wei; Wang, Junfeng; Yuan, Songliu

    2014-08-01

    We report the magnetic, specific heat and electron spin resonance (ESR) studies on Ba3MnNb2O9, as one of quasi-two-dimensional triangula-lattice magnet. The magnetic susceptibility and specific heat measurement show that it undergoes an magnetic transition at TN=3.2 K. The magnetic capacity (Cmag) follows T2 dependence, and magnetic entropy (Smag) reaching to 14.5 J K-1mol-1 at 32 K satisfactorily agrees with the theoretical estimations of Mn2+ ion in high-spin configuration with S=5/2. From the ESR spectra, the Landé factor (geff), the linewidth (ΔHpp) and the ESR intensity (I) are derived and analyzed as a function of temperature. As temperature decreases to T*~18 K, the g-factor shows a minima with geff=1.984(2) before shifts to larger value at lower temperatures, and the ESR intensity starts to be suppressed below this temperature. This anomalous phenomenon is explained in terms of the establishment of short-range AFM spin correlations at much higher temperatures above TN.

  11. Superoxide release by confluent endothelial cells, an electron spin resonance (ESR) study

    NASA Astrophysics Data System (ADS)

    Barbacanne, M.-A.; Margeat, E.; Arnal, J.-F.; Nepveu, F.; Souchard, J.-P.

    1999-01-01

    In the present study we used ESR to detect the release of oxygen radicals by endothelial cells stimulated with calcium ionophore A23187. Dimethyl-1-pyrroline-N-oxide (DMPO) was used as a spin trap. Although the observed adduct (DMPO-OH) suggested the presence of the hydroxyl radical, the use of superoxide dismutase and catalase revealed that superoxide anion was released in the medium. Superoxide production was more efficient when the cells were post-confluent for a few days. The release of superoxide was 3-fold greater in growth arrested cells (D6-D9) than in proliferating cells (D0). Although two inhibitors of the mitochondrial respiratory chain carbanyl cyanide m-chlorophenylhydrazone (CCCP), antimycine decreased the ESR signal by 35%, the use of superoxide dismutase (SOD) and tumor necrosis factor (TNF) suggested that the release of O2- occurred in the cell membrane. The physiological significance of this extracellular superoxide release by post-confluent cells deserves further study. Ce travail présente une étude par RSE de la libération des radicaux oxygénés par les cellules endothéliales bovines (BAEC) sous l'effet de l'ionophore calcique A23187. Le diméthyl-1-pyrroline-N-oxyde (DMPO) est utilisé comme piégeur de spin. Bien que l'adduit formé (DMPO-OH) semble traduire la présence du radical hydroxyle .OH, l'utilisation de superoxyde dismutase et de catalase a révélé que les cellules endothéliales libéraient l'anion superoxyde. La production du radical superoxyde est plus abondante lorsque les cellules sont à confluence depuis plusieurs jours. Lorsque les cellules sont entre J6 et J9, la production de superoxyde est trois fois supérieure à celle observée lorsque les cellules sont en prolifération (J0). Bien que deux inhibiteurs de la chaîne mitochondriale 1-carbonyldinitrile-m-chlorophenylhydrazone (CCCP), antimycineinhibent de 35 % le signal RPE, l'utilisation de superoxyde dismutase (SOD) et du tumor necrosis factor (TNF) sugg

  12. Free radicals and SOD activity of jaw cyst. Direct measurement and spin trapping studies by ESR.

    PubMed

    Kimura, H; Simodate, H; Suzuki, M

    1990-01-01

    Free radicals produced in the fluid of jaw cysts were directly measured at room temperature using ESR. With these samples, SOD activity of the cyst fluid was measured by the ESR spin trapping method with DMPO as a trapping agent. Freeze-dried samples of cyst fluid showed a broad ESR signal at g = 2.005. Relative signal intensity of samples from jaw cysts with inflammation was higher than jaw cysts without inflammation. SOD activity of cyst fluid with high viscosity showed higher values than that of cyst fluid with low viscosity. We suggest that free radicals produced in jaw cyst damage tissues while higher SOD activity of cyst fluid play a role in a self-defense mechanism against free radicals. PMID:2167266

  13. ESR dosimetry study of population in the vicinity of the Semipalatinsk Nuclear Test Site

    PubMed Central

    Zhumadilov, Kassym; Ivannikov, Alexander; Stepanenko, Valeriy; Zharlyganova, Dinara; Toyoda, Shin; Zhumadilov, Zhaxybay; Hoshi, Masaharu

    2013-01-01

    A tooth enamel electron spin resonance (ESR) dosimetry study was carried out with the purpose of obtaining the individual absorbed radiation doses of population from settlements in the Semipalatinsk region of Kazakhstan, which was exposed to radioactive fallout traces from nuclear explosions in the Semipalatinsk Nuclear Test Site and Lop Nor test base, China. Most of the settlements are located near the central axis of radioactive fallout trace from the most contaminating surface nuclear test, which was conducted on 29 August 1949, with the maximum detected excess dose being 430 ± 93 mGy. A maximum dose of 268 ± 79 mGy was determined from the settlements located close to radioactive fallout trace resulting from surface nuclear tests on 24 August 1956 (Ust-Kamenogorsk, Znamenka, Shemonaikha, Glubokoe, Tavriya and Gagarino). An accidental dose of 56 ± 42 mGy was found in Kurchatov city residents located close to fallout trace after the nuclear test on 7 August 1962. This method was applied to human tooth enamel to obtain individual absorbed doses of residents of the Makanchi, Urdzhar and Taskesken settlements located near the Kazakhstan–Chinese border due to the influence of nuclear tests (1964–1981) at Lop Nor. The highest dose was 123 ± 32 mGy. PMID:23404205

  14. Activation of the anticancer drug CCNU into a free radical intermediate via UV irradiation--an ESR study.

    PubMed

    Raikov, Z D; Zheleva, A M; Raikova, E T

    1990-01-01

    We studied the formation of a free radical induced by UV irradiation of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea (CCNU) in benzene. It was determined a stable nitroxide radical by ESR spectroscopy. We confirmed that sterically hindered cyclic amine 2,2,6,6-tetramethyl-4-piperidone (TMPone) was transformed into a corresponding stable free nitroxyl radical during UV irradiation. When CCNU was present, the rate of free radical formation from TMPone increased considerably. PMID:1963416

  15. Permeability studies of redox-sensitive nitroxyl spin probes in corn oil using an L-band ESR spectrometer

    NASA Astrophysics Data System (ADS)

    Jebaraj, D. David; Utsumi, Hideo; Asath, R. Mohamed; Benial, A. Milton Franklin

    2016-05-01

    Electron spin resonance (ESR) studies were carried out for 2mM 14N labeled 2H enriched 3-methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (MC-PROXYL) and 3-carboxy-2,2,5,5,-tetramethyl-1-pyrrolidinyloxy (carboxy-PROXYL) in pure water and various concentrations of corn oil. The ESR parameters, such as the line width, hyperfine coupling constant, g-factor, rotational correlation time, partition parameter and permeability were reported for the samples. The line width broadening was observed for both nitroxyl radicals in corn oil solutions. The partition parameter for permeable MC-PROXYL in corn oil increases with increasing concentration of corn oil, which reveals that the nitroxyl spin probe permeates into the oil phase. From the results, the corn oil concentration was optimized as 50 % for phantom studies. The rotational correlation time also increases with increasing concentration of corn oil. The permeable and impermeable nature of nitroxyl spin probes was demonstrated. These results will be useful for the development of ESR/OMR imaging modalities in in vivo and in vitro studies.

  16. ESR spin trapping study of the effect of oxidative stress and dietary Zn deficiency on free radical production in vivo

    SciTech Connect

    Xu, Z.; Chen, G.; Bray, T.M. )

    1991-03-15

    The objective of this study is to examine if free radicals can be trapped in vivo in dietary Zn deficient rats using ESR spin trapping techniques. The ability of Zn deficient rats to cope with oxidative stress is also assessed. {alpha}-Phenyl-N-t-butyl-nitrone (PBN), a spin trap, was i.p injected at a dose of 75 mg or 150 mg/kg body weight. The tissue distribution and metabolism of PBN in Zn deficient, pair-fed and control rats were compared. ESR signals in liver and lung were used as a measure of free radicals generated in vivo. When the rats were challenged with free radical generating agents, CCl{sub 4}, or FeNTA, the intensity of ESR signal recorded from the Zn deficient rats was about 50% and 30% of its pair-fed and ad libitum control, respectively. Under other oxidative stress, such as exposure to ethanol and hyperoxia, there was a higher production of free radicals in the Zn deficient rats compared to its control. These results suggest that dietary Zn deficiency may either increase the susceptibility or reduce the defense ability of the animal to increased oxidative stress.

  17. ESR study of molecular orientation and dynamics of TEMPO derivatives in CLPOT 1D nanochannels.

    PubMed

    Kobayashi, Hirokazu; Furuhashi, Yuta; Nakagawa, Haruka; Asaji, Tetsuo

    2016-08-01

    The molecular orientations and dynamics of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical derivatives with large substituent groups at the 4-position (4-X-TEMPO) in the organic one-dimensional nanochannels within the nanosized molecular template 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) were examined using ESR. The concentrations of guest radicals, including 4-methoxy-TEMPO (MeO-TEMPO) or 4-oxo-TEMPO (TEMPONE), in the CLPOT nanochannels in each inclusion compound (IC) were reduced by co-including 4-substituted-2,2,6,6-tetramethylpiperidine (4-R-TEMP) compounds at a ratio of 1 : 30-1 : 600. At higher temperatures, the guest radicals in each IC underwent anisotropic rotational diffusion in the CLPOT nanochannels. The rotational diffusion activation energy, Ea , associated with MeO-TEMPO or TEMPONE in the CLPOT nanochannels (6-7 kJ mol(-1) ), was independent of the size and type of substituent group and was similar to the Ea values obtained for TEMPO and 4- hydroxy-TEMPO (TEMPOL) in our previous study. However, in the case in which TEMP was used as a guest compound for dilution (spacer), the tilt of the rotational axis to the principal axis system of the g-tensor, and the rotational diffusion correlation time, τR , of each guest radical in the CLPOT nanochannels were different from the case with other 4-R-TEMP. These results indicate the possibility of controlling molecular orientation and dynamics of guest radicals in CLPOT ICs through the appropriate choice of spacer. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27001507

  18. Quantification of Randomly-methylated-{beta}-cyclodextrin effect on liposome: An ESR study

    SciTech Connect

    Grammenos, A.; Bahri, M.A.; Guelluy, P.H.; Piel, G.; Hoebeke, M.

    2009-12-04

    In the present work, the effect of Randomly-methylated-{beta}-cyclodextrin (Rameb) on the microviscosity of dimyristoyl-L-{alpha} phosphatidylcholine (DMPC) bilayer was investigated using the electron spin resonance (ESR) technique. The ability of Rameb to extract membrane cholesterol was demonstrated. For the first time, the percentage of cholesterol extracted by Rameb from cholesterol doped DMPC bilayer was monitored and quantified throughout a wide Rameb concentration range. The effect of cholesterol on the inner part of the membrane was also investigated using 16-doxyl stearic acid spin label (16-DSA). 16-DSA seems to explore two different membrane domains and report their respective microviscosities. ESR experiments also establish that the presence of 30% of cholesterol in DMPC liposomes suppresses the jump in membrane fluidity at lipids phase-transition temperature (23.9 {sup o}C).

  19. ESR studies of the slow tumbling of vanadyl spin probes in nematic liquid crystals

    NASA Technical Reports Server (NTRS)

    Eastman, M. P.; Bruno, G. V.; Lawson, J. O.

    1977-01-01

    ESR line shapes that are appropriate for slowly tumbling vanadyl spin probes in viscous nematic liquid crystals were calculated by the stochastic Liouville method. Because of the symmetry possessed by vanadyl, the analysis and interpretation of these line shapes was simplified considerably. Spectral line shapes agreed well with experimental spectra of VOAcAc in the nematic liquid crystal Phase V and BEPC. Deviations from Brownian rotational diffusion were noted. A slowly fluctuating torque analysis yielded good agreement with the experimental spectra.

  20. An ESR study at 4 K of the reaction between H and Ni(CO)4

    NASA Astrophysics Data System (ADS)

    Morton, J. R.; Preston, K. F.

    1984-12-01

    A new ESR spectrum has been generated by the photolysis at 4 K of Kr matrices containing HI and Ni(CO)4. Analysis of the nuclear hyperfine structure for 1H, 2H, 61Ni, and 13C leads to its assignment to the radical HNi(CO)3 which has trigonal geometry and a 2A1 ground state in C3v symmetry.

  1. Study of one-dimensional electron hopping and its effects on ESR line shape

    SciTech Connect

    Tang, Jau; Dikshit, S.N.; Norris, J.R. |

    1997-08-01

    Random hopping processes between discrete sites along a finite open chain or around a closed finite loop are examined. Closed form formulae are prescribed for the dependence of the ESR (electron spin resonance) line shape on the chain length and hopping rate. Significant differences between the closed loop and open chain are demonstrated. Deviation at short time from the results of diffusion in a continuum is presented.

  2. Differential roles of estrogen receptors, ESR1 and ESR2, in adult rat spermatogenesis.

    PubMed

    Dumasia, Kushaan; Kumar, Anita; Deshpande, Sharvari; Sonawane, Shobha; Balasinor, N H

    2016-06-15

    Estrogens, through their receptors, play an important role in regulation of spermatogenesis. However, the precise role of the estrogen receptors (ESR1 and ESR2) has been difficult to determine as in vivo estradiol treatment would signal through both the ESRs. Hence we had developed in vivo selective ESR agonist administration models in adult male rats to decipher the individual roles of the ESRs. Treatment with both ESR1 and ESR2 agonists decreased sperm counts after 60 days of treatment. The present study aimed to delineate the precise causes of decreased sperm counts following treatment with the two ESR agonists. Treatment with ESR1 agonist causes an arrest in differentiation of round spermatids into elongated spermatids, mainly due to down-regulation of genes involved in spermiogenesis. ESR2 agonist administration reduces sperm counts due to spermiation failure and spermatocyte apoptosis. Spermiation failure observed is due to defects in tubulobulbar complex formation because of decrease in expression of genes involved in actin remodelling. The increase in spermatocyte apoptosis could be due to increase in oxidative stress and decrease in transcripts of anti-apoptotic genes. Our results suggest that the two ESRs regulate distinct aspects of spermatogenesis. ESR1 is mainly involved with regulation of spermiogenesis, while ESR2 regulates spermatocyte apoptosis and spermiation. Activation of estrogen signaling through either of the receptors can affect their respective processes during spermatogenesis and lead to low sperm output. Since many environmental estrogens can bind to the two ESRs with different affinities, these observations can be useful in understanding their potential effects on spermatogenesis. PMID:27004961

  3. ESR study of MMA polymerization by a peroxide/amine system: bone cement formation.

    PubMed

    Oldfield, F F; Yasuda, H K

    1999-03-15

    Electron spin resonance (ESR) spectroscopy was used to gain insight at the molecular level into the curing of bone cement. Methyl methacrylate was polymerized using a N,N-dimethyl-p-toluidine (TD)/benzoyl peroxide (BPO) redox system in the presence of polymethyl methacrylate (PMMA) powder. The conventional nine-line ESR spectrum for the growing polymer radical was detected at the gel stage of polymerization. While the optimum free radical concentration was observed near the equimolar amine/BPO concentration, excess amine led to a change in the chemical structure of the trapped radical and inhibited the polymerization process. At a high amine/BPO ratio the nine-line signal disappeared and a three-line nitroxide-based radical appeared. The appearance of this nitroxide signal seems to depend on the amine/BPO molar ratio and on the presence of PMMA. An excess amount of amine with respect to BPO was found to inhibit the polymerization process. When BPO was removed, the system still polymerized but with a longer gelation time and a lower radical concentration. These results demonstrate that trapped free radicals in the bulk polymerization of MMA convert to polymeric peroxides that act as initiators in bone cement. When the accelerator 4-dimethylamino phenethyl alcohol (TDOH) was used, a higher radical concentration was observed in the polymerizing system. TDOH shows potential for being a more effective accelerator than TD for bone cement curing. PMID:10397948

  4. Photochemical synthesis of simple organic free radicals on simulated planetary surfaces - An ESR study

    NASA Technical Reports Server (NTRS)

    Tseng, S.-S.; Chang, S.

    1975-01-01

    Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.

  5. Mn doping effect on optical and ESR studies of Zn1-xMnxO compound sintered at different temperatures

    NASA Astrophysics Data System (ADS)

    Mahule, T.; Srinivasu, V. V.; Das, J.

    2016-05-01

    Polycrystalline bulk samples of Zn1-xMnxO with x=0.02, 0.04, 0.05 and sintered at different temperatures (500 °C & 800 °C) were studied to investigate the doping effect on the structural, optical properties and spin dynamics in ZnO system. The crystallite size was seen to decrease with no significant change in other structural parameters. FTIR study showed a small effect on the Zn-O stretching bond and other bonds due to presence of Mn. Calculation from UV-Vis spectra showed increase in the optical band gap in the low temperature sintered samples due to Mn doping. In the PL spectra, the UV emission seen to dominate for the 500 °C sintered sample, for 800 °C sample the visible emission dominate indicating increase in non-radiative emission. ESR signals obtained from the microwave absorption shows ferromagnetic signal for the low temperature sintered sample only with a g value of 2.004 for the 2% Mn doped sample. The number of spin participation for resonance is calculated from the ESR signal, which supports the magnetic behaviour of this particular sample.

  6. Vitamin E analogue Trolox C. E.s.r. and pulse-radiolysis studies of free-radical reactions.

    PubMed Central

    Davies, M J; Forni, L G; Willson, R L

    1988-01-01

    The reactions between Trolox C, a water-soluble vitamin E analogue, and several oxidizing free radicals including the hydroxyl radical and various peroxy radicals were examined by using the pulse-radiolysis technique. The results demonstrate that Trolox C may undergo rapid one-electron-transfer reactions as well as hydrogen-transfer processes; the resulting phenoxyl radical is shown to be relatively stable, in common with the phenoxyl radical derived from vitamin E. The reactions between the Trolox C phenoxyl radical and a variety of biologically relevant reducing compounds were examined by using both pulse radiolysis and e.s.r. The results demonstrate that the Trolox C phenoxyl radical is readily repaired by ascorbate (k = 8.3 x 10(6) dm3.mol-1.s-1) and certain thiols (k less than 10(5) dm3.mol-1.s-1) but not by urate, NADH or propyl gallate. Evidence from e.s.r. studies indicates that thiol-containing compounds may also enter into similar repair reactions with the alpha-tocopherol phenoxyl radical. Kinetic evidence is presented that suggests that Trolox C may 'repair' proteins that have been oxidized by free radicals. PMID:2849418

  7. Vinylogous tetrathiafulvalene (TTF) {pi}-electron donors and derived radical cations: ESR spectroscopic, magnetic, and X-ray structural studies

    SciTech Connect

    Bryce, M.R.; Moore, A.J.; Tanner, B.K.

    1996-06-01

    The properties of new 2,2`-ethanediylidene(1,3-diethile) derivatives 5, 6 and 8-11 are reported. Cyclic voltammetric studies establish that they are efficient donor molecules, with the extended conjugation resulting in stabilization of dications, relative to tetrathiafulvalene TTF (1). Radical cations are generated by oxidation of the neutral compounds with trifluoroacetic acid or anhydrous silver perchlorate in dichloromethane, and their ESR and proton ENDOR spectra are reported. The bulk of the spin population resides in the central S{sub 2} {double_bond}C-C{double_bond}CS{sub 2} part of the {pi}-system. The X-ray crystal structure of donor 6 reveals that the 2,2`-ethanediylidene(1,3-dithiole) framework is planar. Donor 6 forms a crystalline 1:1 charge-transfer complex with TCNQ, the X-ray crystal structure of which shows a mixed stack structure. A solution of this complex in acetonitrile exhibits ESR spectra of both radical ions, 6{sup {lg_bullet}}{sup +} and TCNQ{sup {lg_bullet}}{sup +}. Static susceptibility data are reported for TCNQ complexes of some of these donors. 20 refs., 9 figs., 7 tabs.

  8. ESR and spin trapping study of. gamma. -irradiated aqueous hydantoin solutions. Keto-enol equilibrium and post-radiolysis growth

    SciTech Connect

    Makino, K.; Mossoba, M.M.; Riesz, P.

    1983-09-01

    An air-saturated aqueous hydantion soluton was ..gamma..-irradiated in the presence of the spin trap 2-methyl-2-nitrosopropane(MNP). The ESR spectrum of the spin adduct produced from hydantoin was assigned to the structure NH-C(=O)-NH-C(=O)-CH-N(O)-/sup t/Bu (I). When the pH was raised from 9.7 to 12.5, it was found that the structure of the spin adduct changes to N=C(O/sup -/)-N=C(OH)-CH-N(O)-/sup t/Bu and that this change is reversible. This spectral change was investigated as a function of pH, and the pK value for the equilibrium was found to be about 11.5. The post-radiolysis growth of the ESR signal was observed for the spin adduct I and di-t-butyl nitroxide, which is produced in the same solution, and was markedly pH dependent. The mechanism for this growth is the same as that previously found in a photolysis study of aqueous MNP solutions.

  9. ESR-ENDOR studies of x-irradiated glucose-1-phosphate dipotassium salt

    NASA Astrophysics Data System (ADS)

    Locher, Sarah E.; Box, Harold C.

    1980-01-01

    Single crystals of the dipotassium salt of gluocose-1-phosphate were grown out of water or deuterium oxide and x-irradiated at 4.2 °K. The products of irradiation were identified by means of ESR and ENDOR spectroscopy. In crystals grown out of water, three different alkoxy radicals were observed as oxidation products. In partially deuterated crystals only one of the aforementioned alkoxy radicals was produced. A hydroxyalkyl radical, RHĊOH was also produced by loss of hydrogen from the C6' position. Electrons trapped at intermolecular sites were identified. The distances between the electron and the protons of the polar hydroxy groups forming the trap were deduced from ENDOR measurements and found to be relatively large, namely 1.732 and 1.738 Å.

  10. Magnetic order and electronic properties of Li2Mn2(MoO4)3 material for lithium-ion batteries: ESR and magnetic susceptibility studies

    NASA Astrophysics Data System (ADS)

    Suleimanov, N. M.; Prabaharan, S. R. S.; Khantimerov, S. M.; Nizamov, F. A.; Michael, M. S.; Drulis, H.; Wisniewski, P.

    2016-08-01

    We describe the application of electron spin resonance (ESR) and magnetic susceptibility methods to study the magnetic properties and valence state of transition metal ions in Li2Mn2(MoO4)3 polyanion compound previously studied for its cathode-active properties in lithium containing batteries. ESR measurements of Li2Mn2(MoO4)3 have shown the presence of Mn2+ ions in the octahedral environment of oxygen ions. It is found that the part of manganese ions occupy the anti-site positions in lithium sublattice. The absence of the ESR signal from molybdenum ions indicates that they are non-magnetic and adopt the 6+ valence state. Considerable overlapping between 3d orbitals of transition metal and 2p oxygen orbitals has been experimentally established. This leads to the indirect exchange interaction and antiferromagnetic ordering of manganese ions at 1.4 K.

  11. Enzyme activity and structural dynamics linked to micelle formation: a fluorescence anisotropy and ESR study.

    PubMed

    Chin, Michael; Somasundaran, Ponisseril

    2014-01-01

    Activities of the enzymes, protease subtilisin and horse radish peroxidase (HRP) have been increased 50 and 40%, respectively, in the presence of the nonionic surfactant, alkyl polyglucoside, compared with the activities in buffer alone. This enzyme hyperactivity reaches a peak at 3.0 mm of surfactant. Investigation into the structure of surfactant aggregates indicates "giant" micelle superstructures at this range of surfactant concentration of 1.7 μm in diameter--dramatically decreasing to 60 and 70 nm at higher surfactant concentrations, while surface tension measurements indicate two critical micelle concentration inflection points at 0.2 and 5.0 mm, which suggests transitions in micelle structure with respect to concentration. Furthermore, electron spin resonance (ESR) indicates that the micelles in first critical micelle concentration regime are loosely packed relative to the second aggregate phase. We hypothesize that this loose packing results in diminished hydration shell repulsion between the micelles, leading to the large, micrometer-sized aggregates. We further hypothesize that it is the interaction with these loosely packed micelles that affects the flexibility of the HRP and protease enzyme structure. Time-resolved fluorescence anisotropy of subtilisin in Brij-30 indicates increasing flexibility of catalytic active site with surfactant concentration. This is correlated with an increase in enzymatic activity. PMID:24303849

  12. Synthesis, structure and ESR studies of Mg doped ZnAlO nanoparticles

    NASA Astrophysics Data System (ADS)

    Cakiroglu, O.; Acikgoz, M.; Arda, L.; Akcan, D.; Dogan, N.

    2015-01-01

    Zn0.98-xMgxAl0.02O solutions with different (x=0.05, 0.10, 0.15, and 0.20) compositions were synthesized by the sol-gel technique using Zn, Mg and Al based alkoxide. The effects of highly Mg doping ratio on structure and magnetic properties were investigated systematically. The phase and the crystal structure of the Zn0.98-xMgxAl0.02O nanoparticles were characterized using X-ray diffraction. Scanning Electron Microscope and X-ray diffraction were utilized to understand the size and microstructure of samples. We observed the particle sizes of nanoparticles between 80 nm and 100 nm range. Furthermore, ESR spectra of Zn0.98-xMgxAl0.02O nanoparticles were collected at room temperature on a Bruker EMX model X-band spectrometer operating at a frequency of 9.50 GHz. It is observed that the critical concentration of Mg, x=0.1, has minimum g-factor and maximum line-width (W).

  13. ESR, optical absorption, and luminescence studies of the peroxy-radical defect in topaz

    SciTech Connect

    Priest, V.; Cowan, D.L. ); Yasar, H.; Ross, F.K. , University of Missouri-Columbia, Columbia, Missouri )

    1991-11-01

    Fast-neutron irradiation of natural topaz crystals produces a single paramagnetic radiation damage center in high concentration. ESR of this center shows a holelike spectrum with {ital S}=1/2 and a strongly anisotropic {ital g} tensor: {ital g}{sub {ital x}{ital x}}=2.0027, {ital g}{sub {ital y}{ital y}}=2.0055, and {ital g}{sub {ital z}{ital z}}=2.0407. We identify this defect as an intrinsic O{sub 2}{sup {minus}} center in the form of a peroxy radical. The orientation of the {ital g} tensor helps confirm this assignment, as does the extraordinary thermal stability; annealing temperatures near 800 {degree}C are required for complete removal. Two uv absorption bands are associated with the peroxy radical, each with oscillator strength near 0.09. Pumping in the higher energy band leads to a polarization-sensitive 2.5-eV luminescence; the other uv band apparently relaxes nonradiatively.

  14. Effect of ultrasound and ionizing radiation on a sterically hindered cyclic secondary amine: an ESR study.

    PubMed

    Kondo, T; Riesz, P

    1991-07-01

    The possible use of 2,2,6,6-tetramethyl-4-piperidone (TMPone) for the detection of singlet oxygen was investigated by gamma radiolysis and sonolysis of oxygen-saturated aqueous solutions. Formation of 2,2,6,6-tetra-methyl-4-piperidone-N-oxyl (TAN) was observed with both gamma radiolysis and sonolysis with a similar dependence on the concentration of TMPone up to 20 mM and a strong dependence on pH. In oxygen-saturated solutions the sonolysis of TMPone leads to the formation of the cyclic hydroxylamine (approx. 30% of the yield of TAN) while radiolysis does not. In the low pH range (5-6.5) and at high concentrations of OH radical scavengers (azide or formate), TAN is produced by sonolysis but not by radiolysis. Sonolysis of argon-saturated solutions of TMPone produces methyl radicals due to the high-temperature regions of the collapsing cavitation bubbles. The methyl radicals were detected by ESR (electron spin resonance) and spin trapping with 3,5-dibromo-2,6-dideuterio-4-nitroso-benzene sulfonate. Since the reaction of singlet oxygen with TMPone is also strongly dependent on pH, it does not seem likely that TMPone could be used for the detection of singlet oxygen in sonochemistry. PMID:1648754

  15. ESR dosimetry study on population of settlements nearby Ust-Kamenogorsk city, Kazakhstan.

    PubMed

    Zhumadilov, Kassym; Ivannikov, Alexander; Zharlyganova, Dinara; Zhumadilov, Zhaxybay; Stepanenko, Valeriy; Apsalikov, Kazbek; Ali, Mohd Rodzi; Zhumadilova, Anara; Toyoda, Shin; Endo, Satoru; Tanaka, Kenichi; Okamoto, Tetsuji; Hoshi, Masaharu

    2009-11-01

    The method of electron spin resonance (ESR) dosimetry has been applied to human tooth enamel, to obtain individual absorbed doses of residents of settlements in vicinity of Ust-Kamenogorsk city, Kazakhstan (located about 400 km to the east from the epicenter of explosion at the Semipalatinsk Nuclear Test Site, SNTS). This region developed as a major mining and metallurgical center during the Soviet period (uranium production). Most of the investigated settlements (Ust-Kamenogorsk city, Glubokoe, Tavriya, Gagarino) are located near the central axis of the radioactive fallout trace that originated from the surface nuclear test on 24 August 1956, while the Kokpekty settlement (located 400 km to the Southeast from SNTS) was chosen as a control because it was not subjected to any radioactive contamination. In total, 44 samples were measured. It was found that the excess doses obtained after subtraction of natural background radiation ranged up to about 114 mGy for residents of Ust-Kamenogorsk city, whose tooth enamel was formed before 1956. For residents of Gagarino, excess doses did not exceed 47 mGy for all ages. For residents of Tavriya, the maximum excess dose was 54 mGy, while for residents of Glubokoe it was about 58 mGy. For the population of the Shemonaikha settlements located at a distance of about 70 km from the central axis of the radioactive fallout trace, highest excess doses were 110 mGy. These high doses may be due to the influence of uranium enterprises located in that region, but probably not due to dental X-ray irradiation. For a final conclusion on the radiological situation in this region, the number of samples was too small and, therefore, more work is required to obtain representative results. PMID:19557425

  16. Well-studied Cu-BTC still serves surprises: evidence for facile Cu2+/Cu+ interchange

    SciTech Connect

    Szanyi, Janos; Daturi, Marco; Clet, Guillame; Baer, Donald R.; Peden, Charles HF

    2012-03-08

    Cu-BTC (also known as HKUST-1) is a well-characterized Metal Organic Framework material produced in industrial scale and widely studied for a number of potential applications by the scientific community. The co-existence of Cu+ and Cu2+ entities has already been observed in this material, but the presence of Cu+ ions was attributed to oxide impurities. The results presented here clearly demonstrate that Cu+ ions can be present in high concentrations inside the hybrid structure. Furthermore, switching between the two copper oxidation states can be induced by redox treatments, using vacuum and/or reducing gases at different sample temperatures.

  17. Adaptability of ESR dating of fault gouge in aseismic region: A case study on Hangzhou region, China

    NASA Astrophysics Data System (ADS)

    Yao, Qi; Chen, Han-Lin; Zhang, Wei; Ye, Jian-Qing; Liu, Jing-Wei; Zhao, Dong; Niu, Jia-Wen; Liao, Lin

    2008-05-01

    ESR dating has been widely used in seismic assessment. In this paper, we collected fault gouge samples system-atically for ESR (Electron Spin Resonance) dating, and sediment samples of overlying strata, and offset strata for OSL (Optically Stimulated Luminescence) dating along Xiaoshan-Qiuchuan fault (XQF) trending NE-SW, Xiaofeng-Sanmen fault (XSF) trending NW-SE, and Changhua-Putuo fault (CPF) trending E-W. In the same fault outcrop, the ESR data of fault gouge is greater than the OSL data of the strata offset by fault. Therefore, the ESR data of fault gouge colleted in Hangzhou region do not represent the time of weak fault movement in Late Quaternary region, but represent the strong fault movements in Late Cenozoic. The episode of fault movement in Late Cenozoic could be speculated according to the ESR data: 1.00 0.58 Ma, there were strong fault movements along the XSF, XQF and CPF in Hangzhou region; 0.58 0.45 Ma, the fault movements of all faults became weaker and did not zero ESR signals significantly for ESR dating of fault movements; 0.45 0.20 Ma, there were strong fault movements along part of XQF; 0.1 0.01 Ma, there were fault movements along the XSF only, but the fault movements were not strong enough to reset the ESR signal; Since 0.01 Ma, the Hangzhou region tends to be stable. In addition, the XSF might be the division line of fault segmentation of XQF; there were strong fault movements along the southwest segment of XQF during 0.45 Ma to 0.20 Ma; while the fault movements along the northeast segment of XQF mainly occurred during 1.00 0.58 Ma.

  18. ESR1/SYNE1 polymorphism and invasive epithelial ovarian cancer risk: an Ovarian Cancer Association Consortium study

    PubMed Central

    Doherty, Jennifer A.; Rossing, Mary Anne; Cushing-Haugen, Kara L.; Chen, Chu; Van Den Berg, David J.; Wu, Anna H.; Pike, Malcolm C.; Ness, Roberta B.; Moysich, Kirsten; Chenevix-Trench, Georgia; Beesley, Jonathan; Webb, Penelope M.; Chang-Claude, Jenny; Wang-Gohrke, Shan; Goodman, Marc T.; Lurie, Galina; Thompson, Pamela J.; Carney, Michael E.; Hogdall, Estrid; Kjaer, Susanne Kruger; Hogdall, Claus; Goode, Ellen L.; Cunningham, Julie M.; Fridley, Brooke L.; Vierkant, Robert A.; Berchuck, Andrew; Moorman, Patricia G.; Schildkraut, Joellen M.; Palmieri, Rachel T.; Cramer, Daniel W.; Terry, Kathryn L.; Yang, Hannah P.; Garcia-Closas, Montserrat; Chanock, Stephen; Lissowska, Jolanta; Song, Honglin; Pharoah, Paul D.P.; Shah, Mitul; Perkins, Barbara; McGuire, Valerie; Whittemore, Alice S.; Di Cioccio, Richard A.; Gentry-Maharaj, Aleksandra; Menon, Usha; Gayther, Simon A.; Ramus, Susan J.; Ziogas, Argyrios; Brewster, Wendy; Anton-Culver, Hoda; Pearce, Celeste Leigh

    2010-01-01

    We genotyped 13 single nucleotide polymorphisms (SNPs) in the estrogen receptor alpha gene (ESR1) region in three population-based case-control studies of epithelial ovarian cancer conducted in the United States, comprising a total of 1,128 and 1,866 non-Hispanic white invasive cases and controls, respectively. A SNP 19 kb downstream of ESR1 (rs2295190, G-to-T change) was associated with invasive ovarian cancer risk, with a per-T-allele odds ratio (OR) of 1.24 (95% confidence interval (CI), 1.06–1.44, p=0.006). rs2295190 is a non-synonymous coding SNP in a neighboring gene called spectrin repeat containing, nuclear envelope 1 (SYNE1) which is involved in nuclear organization and structural integrity, function of the Golgi apparatus, and cytokinesis. An isoform encoded by SYNE1 has been reported to be downregulated in ovarian and other cancers. rs2295190 was genotyped in an additional 12 studies through the Ovarian Cancer Association Consortium, with 5,279 invasive epithelial cases and 7,450 controls. The per-T-allele OR for this 12-study set was 1.09 (95% CI, 1.02–1.17, p=0.017). Results for the serous subtype in the 15 combined studies were similar to those overall (n=3,545; OR=1.09, 95% CI, 1.01–1.18, p=0.025), and our findings were strongest for the mucinous subtype (n=447; OR=1.32, 95% CI, 1.11–1.58, p=0.002). No association was observed for the endometrioid subtype. In an additional analysis of 1,459 borderline ovarian cancer cases and 7,370 controls, rs2295190 was not associated with risk. These data provide suggestive evidence that the rs2295190 T allele, or another allele in linkage disequilibrium with it, may be associated with increased risk of invasive ovarian cancer. PMID:20056644

  19. Formation of Reactive Sulfite-Derived Free Radicals by the Activation of Human Neutrophils: An ESR Study

    PubMed Central

    Ranguelova, Kalina; Rice, Annette B.; Khajo, Abdelahad; Triquigneaux, Mathilde; Garantziotis, Stavros; Magliozzo, Richard S.; Mason, Ronald P.

    2012-01-01

    The objective of the present study is to determine the effect of (bi)sulfite (hydrated sulfur dioxide) on human neutrophils and the ability of these immune cells to produce reactive free radicals due to (bi)sulfite oxidation. Myeloperoxidase (MPO) is an abundant heme protein in neutrophils that catalyzes the formation of cytotoxic oxidants implicated in asthma and inflammatory disorders. In the present study sulfite (•SO3−) and sulfate (SO4•−) anion radicals are characterized with the ESR spin-trapping technique using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in the reaction of (bi)sulfite oxidation by human MPO and human neutrophils via sulfite radical chain reaction chemistry. After treatment with (bi)sulfite, PMA-stimulated neutrophils produced DMPO-sulfite anion radical, -superoxide, and -hydroxyl radical adducts. The latter adduct probably resulted, in part, from the conversion of DMPO-sulfate to DMPO-hydroxyl radical adduct via a nucleophilic substitution reaction of the radical adduct. This anion radical (SO4•−) is highly reactive and, presumably, can oxidize target proteins to protein radicals, thereby initiating protein oxidation. Therefore, we propose that the potential toxicity of (bi)sulfite during pulmonary inflammation or lung-associated diseases such as asthma may be related to free radical formation. PMID:22326772

  20. In situ ESR study to detect the diffusion of free H and creation of dangling bonds in hydrogenated amorphous silicon

    NASA Astrophysics Data System (ADS)

    Das, U. K.; Yasuda, T.; Yamasaki, S.

    2001-06-01

    In situ electron spin resonance (ESR) was studied during exposure of hydrogenated amorphous silicon (a-Si:H) films to atomic hydrogen (H) generated by a remote plasma. A high diffusion coefficient of free atomic H (>10-10 cm2 s-1) is observed in a-Si:H films at the very initial stage of H treatment. The H creates additional dangling bonds (~1013 cm-2) during in-diffusion. The diffusion mechanism of such free H is a self-limiting process. The dangling bonds created at the very initial stage of H exposure act as the trapping sites for the impinging H atoms. Consequently, the effective diffusion coefficient (Deff) reduces with H treatment time. The Deff for plasma in-diffusion of H with a relatively wide time span reported in literature is considered to be the resultant of the diffusion coefficient of free H and the bonded H. The characteristic depth of dangling-bond distribution decreases with increasing H treatment temperature. The activated rate constants of db creation reactions dominate over the activated free-H diffusion to determine the distribution of additional dangling bonds at different treatment temperatures.

  1. Charge ordering in Nd2/3Ca1/3MnO3: ESR and magnetometry study

    NASA Astrophysics Data System (ADS)

    Polishchuk, D. M.; Tovstolytkin, A. I.; Fertman, E. L.; Desnenko, V. A.; Kravchyna, O.; Khalyavin, D. D.; Salak, A. N.; Anders, A. G.; Feher, A.

    2016-07-01

    The evolution of magnetic and electric properties of the narrow-band manganite Nd2/3Ca1/3MnO3 was studied by the electron-spin resonance (ESR), static magnetic field (dc) and resistivity techniques in the temperature range of 100-380 K. It was found that below the charge ordering temperature, TCO≈212 K, the compound is a mixture of the charge ordered and charge disordered phases in varying proportions depending on the temperature. The exchange phase process, when the amount of the charge ordered phase increases under cooling, while the amount of the charge disordered phase decreases is the most intense between ∼220 K and 180 K. At low temperatures, T<160 K, the charge ordered to the charge disordered phase ratio is about 4:1, which is in excellent agreement with previous neutron diffraction data. Both a sharp decrease of the magnetic susceptibility and a huge resistivity increase are evident of the weakening of ferromagnetic correlations and suppression of the double exchange interaction across the charge ordering due to the localization of the charge carriers.

  2. Efficiency and rate capability studies of the time-of-flight detector for isochronous mass measurements of stored short-lived nuclei with the FRS-ESR facility

    NASA Astrophysics Data System (ADS)

    Kuzminchuk-Feuerstein, Natalia; Fabian, Benjamin; Diwisch, Marcel; Plaß, Wolfgang R.; Geissel, Hans; Ayet San Andrés, Samuel; Dickel, Timo; Knöbel, Ronja; Scheidenberger, Christoph; Sun, Baohua; Weick, Helmut

    2016-06-01

    A time-of-flight (TOF) detector is used for Isochronous Mass Spectrometry (IMS) with the projectile fragment separator FRS and the heavy-ion storage ring ESR. Exotic nuclei are spatially separated in flight with the FRS at about 70% of the speed of light and are injected into the ESR. The revolution times of the stored ions circulating in the ESR are measured with a thin transmission foil detector. When the ions penetrate the thin detector foil, secondary electrons (SEs) are emitted from the surface and provide the timing information in combination with microchannel plate (MCP) detectors. The isochronous transport of the SEs is performed by perpendicular superimposed electric and magnetic fields. The detection efficiency and the rate capability of the TOF detector have been studied in simulations and experiments. As a result the performance of the TOF detector has been improved substantially: (i) The SE collection efficiency was doubled by use of an optimized set of electric and magnetic field values; now SEs from almost the full area of the foil are transmitted to the MCP detectors. (ii) The rate capability of the TOF detector was improved by a factor of four by the use of MCPs with 5 μm pore size. (iii) With these MCPs and a carbon foil with a reduced thickness of 10 μg/cm2 the number of recorded revolutions in the ESR has been increased by nearly a factor of 10. The number of recorded revolutions determine the precision of the IMS experiments. Heavy-ion measurements were performed with neon ions at 322 MeV/u and uranium fission fragments at about 370 MeV/u. In addition, measurements with an alpha source were performed in the laboratory with a duplicate of the TOF detector.

  3. Use of meta-analysis to combine candidate gene association studies: application to study the relationship between the ESR PvuII polymorphism and sow litter size

    PubMed Central

    Alfonso, Leopoldo

    2005-01-01

    This article investigates the application of meta-analysis on livestock candidate gene effects. The PvuII polymorphism of the ESR gene is used as an example. The association among ESR PvuII alleles with the number of piglets born alive and total born in the first (NBA1, TNB1) and later parities (NBA, TNB) is reviewed by conducting a meta-analysis of 15 published studies including 9329 sows. Under a fixed effects model, litter size values were significantly lower in the "AA" genotype groups when compared with "AB" and "BB" homozygotes. Under the random effects model, the results were similar although differences between "AA" and "AB" genotype groups were not clearly significant for NBA and TNB. Nevertheless, the most noticeable result was the high and significant heterogeneity estimated among studies. This heterogeneity could be assigned to error sampling, genotype by environment interaction, linkage or epistasis, as referred to in the literature, but also to the hypothesis of population admixture/stratification. It is concluded that meta-analysis can be considered as a helpful analytical tool to synthesise and discuss livestock candidate gene effects. The main difficulty found was the insufficient information on the standard errors of the estimated genotype effects in several publications. Consequently, the convenience of publishing the standard errors or the concrete P-values instead of the test significance level should be recommended to guarantee the quality of candidate gene effect meta-analyses. PMID:15943920

  4. ESR study on the visible photocatalytic mechanism of nitrogen-doped novel TiO{sub 2}

    SciTech Connect

    Zhang Jiwei; Jin Zhensheng; Feng Caixia; Yu Laigui; Zhang Jingwei; Zhang Zhijun

    2011-11-15

    The visible photocatalytic mechanism of nitrogen-doped novel TiO{sub 2} was studied by means of electron spin resonance spectroscopy (ESR). It was found that, under visible light irradiation, the concentration of single-electron-trapped oxygen vacancy (SETOV, V{sub o}{sup {center_dot}}) of novel TiO{sub 2} remained unchanged, but that of nitrogen-doped novel TiO{sub 2} increased and returned to original state when the light was turned off. This implies that, aside from V{sub o}{sup {center_dot}} in bulk of nitrogen-doped novel TiO{sub 2}, oxygen vacancy without trapped electron (V{sub o}{sup {center_dot}{center_dot}}) was formed on its surface. V{sub o}{sup {center_dot}{center_dot}} as a surface electron trap captured photogenerated electron from the bulk to generate extra V{sub o}{sup {center_dot}}, carrying out photocatalytic reaction on the surface. At the same time, nitrogen doping product NO was chemically adsorbed on the vicinity of V{sub o}{sup {center_dot}{center_dot}} and inhibited the attack of oxygen, allowing V{sub o}{sup {center_dot}{center_dot}} to remain stable in air. The synergistic action of the two kinds of active structures, i.e., bulk V{sub o}{sup {center_dot}}-NO-Ti and surface V{sub o}{sup {center_dot}{center_dot}}-NO-Ti, accounted for the visible photocatalytic activity of N-doped novel TiO{sub 2}. - Graphical abstract: Synergistic action is realized between (V{sub o}{sup {center_dot}}){sub bulk} and (V{sub o}{sup {center_dot}{center_dot}}){sub surf} in the presence of active structures (V{sub o}{sup {center_dot}}){sub bulk}-NO-Ti and (V{sub o}{sup {center_dot}{center_dot}}){sub surf} -NO-Ti. Research Highlights: > The origin of visible photocatalytic activity of the N-TiO{sub 2} was studied by ESR. > (V{sub o}{sup {center_dot}}){sub bulk} and (V{sub o}{sup {center_dot}{center_dot}}){sub surf} formed in N-TiO{sub 2}. > (V{sub o}{sup {center_dot}}){sub bulk} and (V{sub o}{sup {center_dot}{center_dot}}){sub surf} show a synergistic effect in

  5. ESR Studies and HMO Calculations on Benzosemiquinone Radical Anions: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Beck, Rainer; Nibler, Joseph W.

    1989-01-01

    Discusses electron spin resonance, a form of magnetic resonance spectroscopy, used to study electronic structure of molecules with unpaired electrons. Studies benzosemiquinone radical anions which are long-lived and inexpensive. Uses a Project SERAPHIM computer program to perform a Huckel molecular orbital calculation. (MVL)

  6. ESR dating of pseudotachylite

    NASA Astrophysics Data System (ADS)

    Shimada, A.; Toyoda, S.; Takagi, H.; Arita, K.

    2002-12-01

    ESR (electron spin resonance) dating method has been used to determine the ages of quaternary events. When a mineral receives natural radiation, a part of paired electrons in quartz are ionized, and are trapped by lattice defects and impurties as unpaired electrons. The amount of unpaired electrons increases with time. The ESR age is obtained by dividing the total dose of natural radiation by the natural dose rate. Gamma ray doses are given to the sample to obtain the total dose by extrapolating the dose response of the signal intensity to the zero ordinate. The natural dose rate is calculated from U, Th, and K concentrations, and so on. Quartz is one of the promising minerals useful for ESR dating. In the present paper, we attempted to obtain ages of a land slide event. We collected pseudotachylite from Lantan, Himalaya. A land of about 4 km in diameter has found to have slid several kilometers resulting in pseudotachylite at the base. The samples were gently crushed sieved and soaked in 6N HCl for 1 night and then in 20% HF for two hours, but quartz grains were too small to be extracted. However, ESR signals of characteristic quartz were observed. As long as the sample is uniform, it is not crucial to extract pure quartz grains. With the usual procedure of ESR dating, gamma ray irradiation and ESR measurements, we obtained accumulated natural doses of 290 to 450 Gy. The concentrations of radioactive elements, K, U, Th, which give most of the natural dose to quartz grains, were measured by the low background gamma ray spectrometry. We obtained 7.62 ppm of uranium, 21.1 ppm of thorium, and 3.72% of K2O. Assuming the cosmic dose rate of 0.1mGy/y, we obtained 6.08 mGy/y as the natural dose rate. The ESR ages are obtained by dividing the accumulated doses by the natural dose rate to be 49ka from Al center signal (an electronic hole trapped at Al impurity in quartz) and 74ka from Ti center signal (an electron trapped at Ti impurity in quartz) for a sample, and 56ka and

  7. ESR and electrochemical study of 5-nitroindazole derivatives with antiprotozoal activity

    NASA Astrophysics Data System (ADS)

    Olea-Azar, Claudio; Cerecetto, Hugo; Gerpe, Alejandra; González, Mercedes; Arán, Vicente J.; Rigol, Carolina; Opazo, Lucía

    2006-01-01

    The electrochemistry of 3-alkoxy- and 3-hydroxy-1-[ω-(dialkylamino)alkyl]-5-nitroindazole derivatives were characterized using cyclic voltammetry in DMSO. The nitro reduction process was studied and this was affected by the acid moieties present in these compounds. A nitro anion self-protonation process was observed. This phenomenon was studied by cyclic voltammetry in presence of increasing amount of NaOH. The reactivity of the nitro anion radical of these derivatives with glutathione was also studied by cyclic voltammetry. The oxidizing effect of glutathione is supported by the parallel decrease of the anodic peak current and increase of the cathodic peak in the cyclic voltammograms, corresponding to the wave of the nitro anion radical from uncharged species with the addition of glutathione. Nitro anion radicals obtained by electrolytic reduction of these derivatives were measured and analyzed in DMSO using electron spin resonance spectroscopy.

  8. Microscopic ESR study of N@C60 using a Magnetic Resonance Force Microscope

    NASA Astrophysics Data System (ADS)

    Banerjee, P.; Pelekhov, D. V.; Fong, K. C.; Lee, I. H.; Hammel, P. C.; Harneit, W.

    2007-03-01

    We report electron spin resonance studies of the endohedral fullerene N@C60 using the novel technique of magnetic resonance force microscopy (MRFM). These studies are performed at temperatures down to 1 K on both thin films of N@C60 and in samples where the endohedral fullerene is incorporated into a bulk crystalline matrix. Utilizing the large magnetic field gradients (˜ 10^5 Tesla/meter) in the vicinity of our micromagnetic probe tip, we are able to selectively probe the electron spins in sub--micron volumes. Further, our schemes for spin manipulation allow us to measure the spin--lattice relaxation rate (T1-1) with a spatial resolution in one dimension of approximately 20 nanometers. We will also discuss our efforts to improve the sensitivity of our microscope for detecting individual electronic spins. B. Naydenov, C. Spudat, W. Harneit, H. I. Suss, J. Hullinger, J. Nuss, M. Jansen, Chem. Phys. Lett., 424, 327 (2006).

  9. ESR study of the heterogeneous radical decomposition of hydrogen peroxide vapor on glass and silica

    SciTech Connect

    Arutyunyan, A.Z.; Grigoryan, G.L.; Nalbandyan, A.B.

    1986-01-01

    This paper presents the results of a study carried out on the laws governing the accumulation of HO/sub 2/ radicals in the gas phase during the heterogeneous decomposition of hydrogen peroxide vapor on surfaces of Pyrex glass and silica tablets. It was found that for short contact times (10/sup -2/ sec) and low mixture pressures (of the order of several hundred Pa) the decomposition of H/sub 2/O/sub 2/ occurs mainly on the external surface of the tablets. Rates and activation energies were determined for the generation and heterogeneous decay of HO/sub 2/ radicals on these surfaces at 473-623 K. A low activation energy of 4.6 kJ/mole was obtained for the radical decay process.

  10. ESR study of the aziridine and azetidine radical cations: evidence for the C. C ring-opened aziridine radical cation

    SciTech Connect

    Qin, X.Z.; Williams, F.

    1986-05-22

    The radical cations from aziridine and azetidine have been characterized by ESR spectroscopy following their generation in the solid state by ..gamma.. irradiation of dilute solutions of the parent compounds in the CFCl/sub 3/ matrix at 77 K. The ESR parameters of the azetidine radical cation are typical of those for nitrogen-centered amine radical cations such as Me/sub 2/NH*/sup +/. On the other hand, the radical cation formed from aziridine has very different ESR parameters that compare closely to those for the isoelectronic C...C ring-opened form of the oxirane radical cation and the allyl radical. The radical cation formed from azetidine is therefore assigned a ring-closed structure with the unpaired electron in a 2p/sub z/ orbital on nitrogen perpendicular to the ring plane, whereas the cation from aziridine is an allylic C...C ring-opened planar isomer with the unpaired electron in a nonbonding ..pi.. orbital centered mainly on the two end carbon atoms. The neutral 1-aziridinyl and 1-azetidinyl radicals have been detected as radical products following the ..gamma.. irradiation of the parent compounds in the CFCl/sub 2/CF/sub 2/Cl and CF/sub 3/CCl/sub 3/ matrices. In particular, the 1-azetidinyl radical is produced cleanly from the azetidine radical cation in the CFCl/sub 2/CF/sub 2/Cl matrix at ca. 100 K.

  11. Luminescence and ESR studies of relationships between O(-)-centres and structural iron in natural and synthetically hydrated kaolinites

    NASA Technical Reports Server (NTRS)

    Coyne, L. M.; Costanzo, P. M.; Theng, B. K.

    1989-01-01

    Luminescence, induced by dehydration and by wetting with hydrazine and unsymmetrically substituted hydrazine, and related ESR spectra have been observed from several kaolinites, synthetically hydrated kaolinites, and metahalloysites. The amine-wetting luminescence results suggest that intercalation, not a chemiluminescence reaction, is the luminescence trigger. Correlation between hydration-induced luminescence and g = 2 ESR signals associated with O(-)-centres in several natural halloysites, and concurrent diminution of the intensity of both these signal types as a function of aging in two 8.4 angstroms synthetically hydrated, kaolinites, confirm a previously-reported relationship between the luminescence induced by dehydration and in the presence of O(-)-centres (holes, i.e., electron vacancies) in the tetrahedral sheet. Furthermore, the ESR spectra of the 8.4 angstroms hydrate showed a concurrent change in the line shape of the g = 4 signal from a shape usually associated with structural Fe in an ordered kaolinite, to a simpler one typically observed in more disordered kaolinite, halloysite, and montmorillonite. Either structural Fe centres and the O(-)-centres interact, or both are subject to factors previously associated with degree of order. The results question the long-term stability of the 8.4 angstroms hydrate, although XRD does not indicate interlayer collapse over this period. Complex inter-relationships are shown between intercalation, stored energy, structural Fe, and the degree of hydration which may be reflected in catalytic as well as spectroscopic properties of the clays.

  12. ESR studies on the thermal decomposition of trimethylamine oxide to formaldehyde and dimethylamine in jumbo squid (Dosidicus gigas) extract.

    PubMed

    Zhu, Junli; Jia, Jia; Li, Xuepeng; Dong, Liangliang; Li, Jianrong

    2013-12-15

    The effects of ferrous iron, heating temperature and different additives on the decomposition of trimethylamine oxide (TMAO) to formaldehyde (FA) and dimethylamine (DMA) and generation of free radicals in jumbo squid (Dosidicus gigas) extract during heating were evaluated by electron spin resonance (ESR). The thermal decomposition of TMAO to TMA, DMA and FA and free radical signals was observed in squid extract, whereas no DMA, FA and free radical signals were detected in cod extract or in aqueous TMAO solution in vitro at high temperatures. Significant increase in levels of DMA, FA and radicals intensity were observed in squid extract and TMAO solution in the presence of ferrous iron with increasing temperature. Hydrogen peroxide stimulated the production of DMA, FA and ESR signals in squid extract, while citric acid, trisodium citrate, calcium chloride, tea polyphenols and resveratrol had the opposite effect. Similar ESR spectra of six peaks regarded as amminium radical were detected in the squid extract and TMAO-iron(II) solution, suggesting that the amminium radical was involved in the decomposition of TMAO. PMID:23993561

  13. A comparative ESR study of some paramagnetic materials as probes for the noninvasive measurement of dissolved oxygen in biological systems.

    PubMed

    Inoue, M; Utsumi, H; Kirino, Y

    1994-11-01

    The ESR properties of three types of paramagnetic material, active charcoal, fusinite and a stable nitroxide radical 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPONE), were examined in order to evaluate their suitability as probes to measure dissolved intra- and extra-cellular oxygen. Although, with changes in oxygen concentration, a greater change in the linewidth of ESR signals was observed with fusinite or active charcoal, it took a long time (15 min for active charcoal and more than 6 h for fusinite) for equilibrium to be achieved. On the other hand, equilibrium was reached very rapidly in the case of the TEMPONE spectra although the sensitivity to changes in oxygen concentration was only moderate. Furthermore, since lipid bilayers are permeable to TEMPONE, this compound can be used to measure intracellular oxygen concentration when employed in combination with membrane-impermeable spin-broadening reagents which act on ESR signals arising from extracellular probes. A perdeuterated derivative of TEMPONE is useful in that it gives a greater signal-to-noise ratio and greater sensitivity to changes in oxygen concentration. In conclusion, active charcoal is suitable as a probe for extracellular oxygen in a system where changes are slow, while nitroxide is a versatile probe for measuring rapidly changing intra- and extra-cellular oxygen concentrations. PMID:7859334

  14. In situ production of alpha particles and alpha recoil particles in quartz applied to ESR studies of oxygen vacancies

    NASA Astrophysics Data System (ADS)

    Toyoda, S.; Rink, W. J.; Yonezawa, C.; Matsue, H.; Kagami, T.

    2001-12-01

    The intensity of an ESR signal associated with oxygen vacancies in quartz (E 1' center and heat-treated E 1' center) are correlated with the radiometric age of their host rocks. Two natural processes are responsible for the production of oxygen vacancies (1) lattice damage along alpha recoil and alpha particle tracks and (2) randomly distributed ionization damage from energetic electrons (beta particles) and gamma photons. The aim of this paper was to determine whether the track damage process is dominant relative to the ionization processes. Heat-treated E 1' centers are considered a proxy measure of the oxygen vacancy concentration. In situ alpha irradiation of quartz was accomplished by neutron irradiation of lithium and boron-bearing quartz. We found that the oxygen vacancy population measured by ESR was a factor of 2 higher than estimated from calculations of the damage using Ziegler's TRIM software. Considering the uncertainties in absolute determinations of spin concentration from ESR signals, the agreement is very good and supports the theory that alpha particle damage is largely responsible for oxygen vacancy production during natural irradiation of quartz over intervals of hundreds of millions of years.

  15. [ESR study on self-curing resin for rebasing during polymerization].

    PubMed

    Andoh, M

    1989-12-01

    The effects of temperature, concentrations of activator (N, N-dimethyl-p-toluidine) and inhibitor (hydroquinone), atmosphere, liquid powder ratio and mixing time on polymerization process of self-curing resin for rebasing were studied by electron spin resonance. When powder and liquid were mixed at a ratio commercially recommended at a physiologic temperature of 37 degrees C, the propagating radical was first detected 5.5 minutes later, of which time interval corresponds to induction time for polymerization. After the induction time, the concentration of propagating radicals increased rapidly with time and reached the maximum level at 27 minutes. The radicals thus formed remained stable for more than 2.5 days when stored in air at 37 degrees C, though their concentration diminished gradually. With increasing temperature for curing, the maximum level of the radical concentration decreased and the propagating radicals disappeared more rapidly, indicating recombination reactions to be perferentially occurring at higher temperatures. Increase in the amount of activator of N,N-dimethyl-p-toluidine resulted in increase in the radical concentration. When powder was mixed with a liquid containing less inhibitor of hydroquinone, the radicals were found to remain stable longer. In air, propagating radical was detected faster and free radical was concentrated more rapidly than in the water and nitrogen gas. The fluidity of self-cured resin for rebasing as measured by use of spin probe TEMPO disappeared rapidly with increasing temperature for curing, decreasing the amount of liquid and shortening the mixing time. When curing temperature was raised to 37 degrees C from 22 degrees C at minutes after mixing, the fluidity disappeared 2.5 minutes later, i.e., at 5.5 minutes after mixing. To investigate the effects of the MMA-derivative radicals on growth of HeLa cells, HeLa cells were cultured on resins containing MMA-derivative radicals. The number of HeLa cells on resins

  16. ESR spectroscopic properties of irradiated gum Arabic.

    PubMed

    Leonor, S J; Gómez, J A; Kinoshita, A; Calandreli, I; Tfouni, E; Baffa, O

    2013-12-01

    Electron spin resonance (ESR) spectra of irradiated gum Arabic with doses between 0.5 and 5 kGy were studied. A linear relationship between the absorbed dose and the intensities of the ESR spectra was observed. ESR spectra of irradiated gum Arabic showed a decay of relative concentrations of free radicals originated by radiation and the production of at least two species of free radicals with half-times: 3.3 and 125.4 h. The results of spectral simulations for these radical groups were giso=2.0046; A=1.2 mT and gx=gy=2.0062, gz=2.0025. Hydration and dehydration of irradiated gum Arabic returns the ESR spectrum to its initial state before irradiation. The results show that ESR can be used as simple and reliable method to detect irradiated gum Arabic up to 60 days after initial radiation with doses on the order of 5 kGy. PMID:23870902

  17. Studies of gas adsorption on ZnO using ESR, FTIR spectroscopy, and MHE (Microwave Hall Effect) measurements

    SciTech Connect

    Byungki Na; Vannice, M.A. ); Walters, A.B. )

    1993-04-01

    This paper describes the application of a new technique - Microwave Hall Effect (MHE) measurements - to measure electron mobilities and to determine the effect of adsorption on electron densities of powders. Conduction electron densities calculated from microwave measurements of both mobilities and conductivities, as well as ESR spectroscopy and chemisorption measurements, have been applied to characterize high-surface-area ZnO (up to 30 m[sup 2]/g) samples before and after exposure to O[sub 2], CO[sub 2], CO, and H[sub 2]. Evacuation at 673 K removed lattice oxygen to produce paramagnetic lattice vacancies, (V[sub 0][sup +])[sup [minus

  18. An ESR study of the radiation chemistry of poly (tetrafluoroethylene-co-hexafluoropropylene) at 77 and 300 K

    NASA Astrophysics Data System (ADS)

    Hill, David J. T.; Mohajerani, Shahroo; Pomery, Peter J.; Whittaker, Andrew K.

    2000-09-01

    The effect of gamma-irradiation on poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) with a composition of ≈9:1 has been investigated at low doses by Electron Spin Resonance Spectroscopy (ESR). Irradiations have been carried out at 77 and 300 K and the spectra of the radical intermediates have been delineated and the temperature dependencies of the spectra of the major radicals present have been identified. The overall G-values for radical formation at 77 and 300 K were found to be 0.22 ± 0.1 and 2.0 ± 0.1, respectively.

  19. Production of oxygen-centered radicals by neutrophils and macrophages as studied by electron spin resonance (ESR).

    PubMed Central

    Bannister, J V; Bannister, W H

    1985-01-01

    Neutrophils and macrophages undergo a respiratory burst and an increase in the activity of the hexose monophosphate pathway in response to particulate or soluble agents. The increase in oxygen consumption was found to be associated with the production of oxygen-centered radicals. The ESR technique of spin trapping showed that besides a superoxide spin adduct, a hydroxyl spin adduct is also produced. ESR is considered to be the least ambiguous technique for the detection of free radicals. The spin-trapping agents used for oxygen-centered radical detection are usually nitrones. The most commonly used nitrone is 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), which reacts with O2-. to form 5,5-dimethyl-2-hydroperoxypyrroline-N-oxide (DMPO-OOH) and with OH. to form 5,5-dimethyl-2-hydroxypyrroline-N-oxide (DMPO-OH). Although spin-adduct formation is considered to be the most direct technique for the detection of free radicals, some disadvantages are encountered. There has been considerable interest in the isolation of the O2-. generating activity from phagocytic cells. The enzyme can be extracted with deoxycholate and gel filtration indicates that it is a high molecular weight complex. Maximum activity was between pH 7.0 and pH 7.5. The Km value was 15.8 microM for NADPH and 434 micron for NADH, indicating that NADPH is the preferred substrate. PMID:3007099

  20. Probing Polymer-Segment Motions By ESR

    NASA Technical Reports Server (NTRS)

    Tsay, Fun-Dow; Gupta, Amitava

    1988-01-01

    Molecular origins of mechanical properties and aging processes studied. Rotational motions of segments of poly(methyl methacrylate) molecules studied theoretically and experimentally. Activation energies of these motions as determined from temperature dependencies of ESR spectra agree closely with predictions of theory.

  1. ESR Studies of Layered-Perovskite Manganites R0.5Sr1.5MnO4 (R = La, Nd)

    NASA Astrophysics Data System (ADS)

    Marumoto, Kazuhiro; Soda, Kazuya; Kuroda, Shin-ichi; Moritomo, Yutaka

    2003-03-01

    ESR studies have been performed on single crystals of layered-perovskite manganites R0.5Sr1.5MnO4 (R = La, Nd). An anisotropic ESR signal with extremely broad linewidth is observed and ascribed to the single-ion-anisotropic D term. For La0.5Sr1.5MnO4, the spin susceptibility χs deviates from the Curie-Weiss-like behavior and the peak-to-peak linewidth Δ Hpp shows a broad maximum at the charge-ordering temperature Tco (≈ 217 K). With further decrease of temperature below 160 K, χs decreases and Δ Hpp increases rapidly due to the spin order at the Néel temperature TN (≈ 110 K). These anomalies are absent in Nd0.5Sr1.5MnO4, which does not show the charge-ordering nor the spin-ordering. On the basis of these experimental data, we will discuss the charge and spin order of La0.5Sr1.5MnO4.

  2. Radiolysis of carbohydrates as studied by ESR and spin-trapping—II. Glycerol- d8 xylitol, dulcitol, d-sorbitol and d-mannitol

    NASA Astrophysics Data System (ADS)

    Kuwabara, M.; Zhang, Z.-Y.; Inanami, O.; Yoshii, G.

    Studies concerning the radicals produced in glycerol by reactions with OH radicals have been carried out by investigating deuterated glycerol (glycerol-d 8) by spin-trapping with 2-methyl-2-nitrosopropane. Free radicals produced in linear carbohydrates such as xylitol, dulcitol, D-sorbitol and D-mannitol by reactions with OH radicals as well as by direct γ-radiolysis have been also investigated by spin-trapping. The ESR spectra of the spin-trapped radicals were analysed on the basis of the results from ESR and spin-trapping experiments on glycerol and deuterated glycerol, and the formation of three radical species, CHO-CH-, CH 2-CO- and HO-CH-, due to both OH reactions and direct γ-radiolysis was confirmed for all compounds. The presence of a radical, -CO-CH-, was detected for xylitol, D-sorbitol and D-mannitol. General reactions processes induced by OH reactions or γ-radiolysis in the solid state are discussed.

  3. Persistent free radical ESR signals in marine bivalve tissues. [Electron Spin Resonance (ESR)

    SciTech Connect

    Mehlorn, R.J. . Dept. of Materials Science and Mineral Engineering); Mendez, A.T. ); Higashi, R. . Bodega Marine Lab.); Fan, T. )

    1992-08-01

    Freeze-dried homogenates of the oyster Crassostrea rhizophorae collected from waters in Puerto Rico near urban and industrial sites as well as at relatively pristine locations yielded electron spin resonance (ESR) spectra characteristic of free radicals as well as spectral components of transition metal ions, dominated by manganese. The magnitudes of these ESR signals and the concentrations of trace elements (determined by X-ray fluorescence) varied considerably among oyster samples, masking any potential correlation with polluted waters. Laboratory studies were initiated to identify the factors controlling the magnitudes of the tissue free radical ESR signals. Another mollusc, Mytilus californianus collected at the Bodega Marine laboratory in northern California, was fractionated into goneds and remaining tissue. Freeze-dried homogenates of both fractions exhibited ESR signals that increased gradually with time. ESR signals were observed in freeze-dried perchloric acid (PCA) precipitates of the homogenates, delipidated PCA precipitates, and in chloroform extracts of these precipitates. Acid hydrolysis to degrade proteins to amino acids produced a residue, which yielded much larger ESR free radical signals after freeze-drying. Freshly thawed homogenates of Crassostrea rhizophorae also exhibited ESR signals. A laboratory model of copper stress in Crassostrea rhizophorae was developed to study the effect of this transition metal on dssue free radicals. Preliminary results suggested that sublethal copper exposure had little effect on tissue fire radicals, except possibly for a signal enhancement in an oyster fraction that was enriched in kidney granules. Since kidney granules are known to accumulate heavy metals in mussels and probably other marine bivalves, this signal enhancement may prove to be an indicator of free radical processes associated with heavy metal deposition in molluscs.

  4. ESR teleradiology survey: results.

    PubMed

    2016-08-01

    With recent developments of teleradiology technology and services, it has become necessary to better evaluate its extent and use among different countries in Europe. With this goal in mind, the ESR launched two specific surveys intended to gather the current state of adoption and implementation of teleradiology in clinical practice. A special focus on differentiating between insourcing teleradiology services among partners of the same organisation and outsourcing to external services was an essential part of the design of these surveys. The first survey was addressed to 44 national societies of different countries in Europe, while the second survey was intended for all practicing radiologist ESR members. While the results of these surveys reported here may provide a wealth of information to better understand the trends in adoption of teleradiology in Europe, they only represent a snapshot at a certain point in time. The rapid development of telecommunication tools as well as a fundamental change in practice and healthcare economics will certainly influence these observations in the upcoming years. These data, however, will provide objective and relevant parameters for supporting the efforts of experts and policy makers in promoting appropriate criteria and guidelines for adequate use of teleradiology in clinical practice. Main Messages • Understand concepts and challenges of teleradiology • Provide insight into current trends and solutions for teleradiology • Compare differences in teleradiolgy strategies between countries in Europe • Establish a reference on statistical data of usage of teleradiology in Europe. PMID:27188379

  5. Structure of BCl/sub 2/: ESR study of an x-irradiated crystal of BCl/sub 3/

    SciTech Connect

    Franzi, R.; Geoffroy, M.; Lucken, E.A.C.; Leray, N.

    1983-01-15

    X irradiation of a single crystal of boron trichloride at 77 K yields at least two different radicals. A brief exposure to UV irradiation, however, leaves only one radical whose ESR spectrum shows hyperfine coupling from one boron (/sup 10/B, /sup 11/B) and two equivalent chlorine (/sup 35/Cl, /sup 37/Cl) nuclei and which is identified as BCl/sub 2/. The g tensor, /sup 11/B magnetic hyperfine tensor, /sup 35/Cl magnetic and quadrupole hyperfine tensors have been determined and analyzed in terms of the radical's electronic structure. Problems arising in relating the principal direction of the various tensors to the molecular geometry are discussed. BCl/sub 2/ is nonlinear with a ClBCl angle of approximately 122/sup 0/ and with the unpaired electron mainly localized on the boron atom.

  6. ESR response of gamma-irradiated sulfamethazine

    NASA Astrophysics Data System (ADS)

    Çolak, Seyda; Korkmaz, Mustafa

    In the present work, characteristic features of the radiolytical intermediates produced in gamma-irradiated solid sulfamethazine (SMH) were investigated by electron spin resonance (ESR) spectroscopy. The heights of the resonance peaks, measured with respect to the spectrum baseline, were used to monitor microwave saturation, temperature and time-dependent kinetic features of the radical species contributing to the formation of recorded experimental ESR spectra. Three species having different spectroscopic and kinetic features were observed to be produced in gamma-irradiated SMH. SO2, which is the most sensitive group of radiation in the SMH molecule, was found to be at the origin of radiation-produced ionic radical species. Based on the experimental results derived from the present study, the applicability of ESR spectroscopy to radiosterilization of SMH was discussed. In the dose range of interest (0.5-10 kGy), the radiation yield of solid SMH was calculated to be very low (G=0.45) compared with those obtained for sulfonamide aqueous solutions (G=3.5-5.1). Based on these findings, it was concluded that SMH and SMH-containing drugs could be safely sterilized by gamma radiation and that ESR spectroscopy could be successfully used as a potential technique for monitoring their radiosterilization.

  7. On-Chip ESR Measurements of DPPH at mK Temperatures

    NASA Astrophysics Data System (ADS)

    Voesch, Wolfgang; Thiemann, Markus; Bothner, Daniel; Dressel, Martin; Scheffler, Marc

    We study electron spin resonance (ESR) of DPPH at mK temperatures. Here we employ a superconducting coplanar microwave resonator that allows convenient implementation in a dilution refrigerator as well as operation at multiple ESR frequencies, in this case 1.5 GHz, 3.0 GHz, and 4.5 GHz. We find a strong temperature and magnetic field dependence of the ESR of DPPH below 1 K, which is consistent with an antiferromagnetic transition. Our study documents the potential of this on-chip ESR technique for mK experiments and elucidates the possibility to use DPPH as an ESR reference material in this regime.

  8. Kinetic Studies and Mechanism of Hydrogen Peroxide Catalytic Decomposition by Cu(II) Complexes with Polyelectrolytes Derived from L-Alanine and Glycylglycine

    PubMed Central

    Skounas, Spyridon; Methenitis, Constantinos; Pneumatikakis, George; Morcellet, Michel

    2010-01-01

    The catalytic decomposition of hydrogen peroxide by Cu(II) complexes with polymers bearing L-alanine (PAla) and glycylglycine (PGlygly) in their side chain was studied in alkaline aqueous media. The reactions were of pseudo-first order with respect to [H2O2] and [L-Cu(II)] (L stands for PAla or PGlygly) and the reaction rate was increased with pH increase. The energies of activation for the reactions were determined at pH 8.8, in a temperature range of 293–308 K. A suitable mechanism is proposed to account for the kinetic data, which involves the Cu(II)/Cu(I) redox pair, as has been demonstrated by ESR spectroscopy. The trend in catalytic efficiency is in the order PGlygly>PAla, due to differences in modes of complexation and in the conformation of the macromolecular ligands. PMID:20721280

  9. ESR dosimetry for atomic bomb survivors and radiologic technologists

    NASA Astrophysics Data System (ADS)

    Tatsumi-Miyajima, Junko

    1987-06-01

    An individual absorbed dose for atomic bomb (A-bomb) survivors and radiologic technologists has been estimated using a new personal dosimetry. This dosimetry is based on the electron spin resonance (ESR) spectroscopy of the CO 33- radicals, which are produced in their teeth by radiation. Measurements were carried out to study the characteristics of the dosimetry; the ESR signals of the CO 33- radicals were stable and increased linearly with the radiation dose. In the evaluation of the absorbed dose, the ESR signals were considered to be a function of photon energy. The absorbed doses in ten cases of A-bomb victims and eight cases of radiologic technologists were determined. For A-bomb survivors, the adsorbed doses, which were estimated using the ESR dosimetry, were consistent with the ones obtained using the calculations of the tissue dose in air of A-bomb, and also with the ones obtained using the chromosome measurements. For radiologic technologists, the absorbed doses, which were estimated using the ESR dosimetry, agreed with the ones calculated using the information on the occupational history and conditions. The advantages of this method are that the absorbed dose can be directly estimated by measuring the ESR signals obtained from the teeth of persons, who are exposed to radiation. Therefore, the ESR dosimetry is useful to estimate the accidental exposure and the long term cumulative dose.

  10. ESR (Erythrocyte Sedimentation Rate) Test

    MedlinePlus

    ... be used along with other clinical findings, the individual's health history, and results from other laboratory tests. If the ESR and clinical findings match, the health practitioner may be able to confirm ...

  11. ESR modes in a Strong-Leg Ladder in the Tomonaga-Luttinger Liquid Phase

    NASA Astrophysics Data System (ADS)

    Zvyagin, S.; Ozerov, M.; Maksymenko, M.; Wosnitza, J.; Honecker, A.; Landee, C. P.; Turnbull, M.; Furuya, S. C.; Giamarchi, T.

    Magnetic excitations in the strong-leg quantum spin ladder compound (C7H10N)2CuBr4 (known as DIMPY) in the field-induced Tomonaga-Luttinger spin liquid phase are studied by means of high-field electron spin resonance (ESR) spectroscopy. The presence of a gapped ESR mode with unusual non-linear frequency-field dependence is revealed experimentally. Using a combination of analytic and exact diagonalization methods, we compute the dynamical structure factor and identify this mode with longitudinal excitations in the antisymmetric channel. We argue that these excitations constitute a fingerprint of the spin dynamics in a strong-leg spin-1/2 Heisenberg antiferromagnetic ladder and owe its ESR observability to the uniform Dzyaloshinskii-Moriya interaction. This work was partially supported by the DFG and Helmholtz Gemeinschaft (Germany), Swiss SNF under Division II, and ERC synergy UQUAM project. We acknowledge the support of the HLD at HZDR, member of the European Magnetic Field Laboratory (EMFL).

  12. Fundamental studies of methanol synthesis from CO(2) hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001).

    PubMed

    Yang, Yixiong; Evans, Jaime; Rodriguez, Jose A; White, Michael G; Liu, Ping

    2010-09-01

    A combination of experimental and theoretical methods were employed to investigate the synthesis of methanol via CO(2) hydrogenation (CO(2) + 3H(2)--> CH(3)OH + H(2)O) on Cu(111) and Cu nanoparticle surfaces. High pressure reactivity studies show that Cu nanoparticles supported on a ZnO(0001[combining macron]) single crystal exhibit a higher catalytic activity than the Cu(111) planar surface. Complementary density functional theory (DFT) calculations of methanol synthesis were also performed for a Cu(111) surface and unsupported Cu(29) nanoparticles, and the results support a higher activity for Cu nanoparticles. The DFT calculations show that methanol synthesis on Cu surfaces proceeds through a formate intermediate and the overall reaction rate is limited by both formate and dioxomethylene hydrogenation. Moreover, the superior activity of the nanoparticle is associated with its fluxionality and the presence of low-coordinated Cu sites, which stabilize the key intermediates, e.g. formate and dioxomethylene, and lower the barrier for the rate-limiting hydrogenation process. The reverse water-gas-shift (RWGS) reaction (CO(2) + H(2)--> CO + H(2)O) was experimentally observed to compete with methanol synthesis and was also considered in our DFT calculations. In agreement with experiment, the rate of the RWGS reaction on Cu nanoparticles is estimated to be approximately 2 orders of magnitude faster than methanol synthesis at T = 573 K. The experiments and calculations also indicate that CO produced by the fast RWGS reaction does not undergo subsequent hydrogenation to methanol, but instead simply accumulates as a product. Methanol production from CO hydrogenation via the RWGS pathway is hindered by the first hydrogenation of CO to formyl, which is not stable and prefers to dissociate into CO and H atoms on Cu. Our calculated results suggest that the methanol yield over Cu-based catalysts could be improved by adding dopants or promoters which are able to stabilize formyl

  13. ESR identification of gamma-irradiated albendazole

    NASA Astrophysics Data System (ADS)

    Çolak, Seyda

    2010-01-01

    The use of ionizing radiation for sterilization of pharmaceuticals is a well-established technology. In the present work, the spectroscopic and kinetic features of the radicals induced in gamma-irradiated solid albendazole samples is investigated at different temperatures in the dose range of 3-34 kGy by electron spin resonance (ESR) spectroscopy. Irradiation with gamma radiation produced two different radical species in albendazole. They were fairly stable at room temperature but relatively unstable above room temperature, giving rise to an unresolved ESR spectrum consisting of three resonance peaks centered at g=2.0057. Decay activation energies of the contributing radical species were calculated to be 47.8 (±13.5) and 50.5 (±9.7) kJ/mol using the signal intensity decay data derived from annealing studies performed at high temperatures. A linear function of the applied dose was found to best describe the experimental dose-response data. Albendazole does not present the characteristics of good dosimetric materials. However, the discrimination of irradiated albendazole from its unirradiated form was possible even 6 months after storage in normal conditions. Based on these findings, it is concluded that albendazole and albendazole-containing drugs can be safely sterilized by gamma radiation and that ESR spectroscopy could be successfully used as a potential technique for monitoring their radiosterilization.

  14. Synthesis, structural characterization, fluorescence, antimicrobial, antioxidant and DNA cleavage studies of Cu(II) complexes of formyl chromone Schiff bases

    NASA Astrophysics Data System (ADS)

    Kavitha, P.; Saritha, M.; Laxma Reddy, K.

    2013-02-01

    Cu(II) complexes have been synthesized from different Schiff bases, such as 3-((2-hydroxy phenylimino)methyl)-4H-chromen-4-one (HL1), 2-((4-oxo-4H-chromen-3-yl)methylneamino) benzoicacid (HL2), 3-((3-hydroxypyridin-2-ylimino)methyl)-4H-chromen-4-one (HL3) and 3-((2-mercaptophenylimino)methyl)-4H-chromen-4-one (HL4). The complexes were characterized by analytical, molar conductance, IR, electronic, magnetic, ESR, thermal, powder XRD and SEM studies. The analytical data reveal that metal to ligand molar ratio is 1:2 in all the complexes. Molar conductivity data indicates that all the Cu(II) complexes are neutral. On the basis of magnetic and electronic spectral data, distorted octahedral geometry is proposed for all the Cu(II) complexes. Thermal behaviour of the synthesized complexes illustrates the presence of lattice water molecules in the complexes. X-ray diffraction studies reveal that all the ligands and their Cu(II) complexes have triclinic system with different unit cell parameters. Antimicrobial, antioxidant and DNA cleavage activities indicate that metal complexes exhibited greater activity as compared with ligands.

  15. CH4 dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

    NASA Astrophysics Data System (ADS)

    Zhang, Riguang; Duan, Tian; Ling, Lixia; Wang, Baojun

    2015-06-01

    In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH4 dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH4 dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol-1 on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol-1 on RhCu(1 1 1) surface, and to 180.0 kJ mol-1 on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH4 complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH4, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH4 dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the help of Rh on Cu foils may be carried out at relatively low temperatures. Meanwhile, the adsorbed Rh atom is the reaction active center, namely, the CVD growth can be controlled by manipulating the graphene nucleation position.

  16. Theoretical study on the CuH + H. -->. Cu + H/sub 2/ reaction pathway

    SciTech Connect

    Ruiz, M.E.; Garcia-Prieto, J.; Poulain, E.; Ozin, G.A.; Poirier, R.A.; Matta, S.M.; Czismadia, I.G.; Gracie, C.; Novaro, O.

    1986-01-16

    Quite recently, experimental results on the CuH + H ..-->.. Cu + H/sub 2/ thermal matrix phase reaction were reported, indicating that it proceeds with no activation barrier, and no evidence exists for an intermediate CuH/sub 2/ species at 10-13 K. Here the authors present a theoretical study of this reaction using variational and perturbational configuration interaction calculations with a relativistic pseudopotential (PSHONDO-CIPSI) set of programs. The results confirm the lack of a barrier and provide an explanation as to why the CuH/sub 2/ species may not be observed. 11 references, 3 figures, 3 tables.

  17. ROS production in homogenate from the body wall of sea cucumber Stichopus japonicus under UVA irradiation: ESR spin-trapping study.

    PubMed

    Qi, Hang; Dong, Xiu-fang; Zhao, Ya-ping; Li, Nan; Fu, Hui; Feng, Ding-ding; Liu, Li; Yu, Chen-xu

    2016-02-01

    Sea cucumber Stichopus japonicus (S. japonicus) shows a strong ability of autolysis, which leads to severe deterioration in sea cucumber quality during processing and storage. In this study, to further characterize the mechanism of sea cucumber autolysis, hydroxyl radical production induced by ultraviolet A (UVA) irradiation was investigated. Homogenate from the body wall of S. japonicas was prepared and subjected to UVA irradiation at room temperature. Electron Spin Resonance (ESR) spectra of the treated samples were subsequently recorded. The results showed that hydroxyl radicals (OH) became more abundant while the time of UVA treatment and the homogenate concentration were increased. Addition of superoxide dismutase (SOD), catalase, EDTA, desferal, NaN3 and D2O to the homogenate samples led to different degrees of inhibition on OH production. Metal cations and pH also showed different effects on OH production. These results indicated that OH was produced in the homogenate with a possible pathway as follows: O2(-) → H2O2 → OH, suggesting that OH might be a critical factor in UVA-induced S. japonicus autolysis. PMID:26304359

  18. Study on Oxidation of Cu and Cu3Au Surfaces with Hyperthermal Oxygen Molecular Beam

    NASA Astrophysics Data System (ADS)

    Okada, Michio; Teraoka, Yuden

    Corrosion wastes more than a few percent of the world's GDP every year. The initial stage of the corrosion is one of the central topics in material science. The oxidation is one of the major corrosion processes of metals. Thus, the study of the oxidation process on metal surfaces is generally interesting in various fields of science and technology. The growth of a protective thin surface layer, which prevents further oxidation into bulk of a metal, requires the formation of a homogeneous film. One simple way for the protection of underlying metals is surface alloying, combining different substances to form multi-component surfaces. The surface alloying leads to the formation of a protective oxide layer due to the preferential oxidation of one component, possibly with surface segregation. Copper and copper alloys have wide industrial applications, and therefore are of interest for studies of oxidation mechanism, especially in the Cu2O formation. Cu forms the stable Cu2O, while Au does not form a stable oxide and is not soluble into stable Cu2O. Thus, the Cu-Au alloy system is ideal for investigating the effect of alloying on the formation of protective layer against further oxidation into bulk. Here, we introduce our recent comparative studies of the oxidation of Cu(100) and Cu3Au(100) with hyperthermal O2 molecular beam and discuss why Cu3Au(100) is protective against the oxidation.

  19. Spectroscopic Evidence for Covalent Binding of Sulfadiazine to Natural Soils via 1,4-nucleophilic addition (Michael Type Addition) studied by Spin Labeling ESR

    NASA Astrophysics Data System (ADS)

    Aleksandrova, Olga

    2015-04-01

    Among different classes of veterinary pharmaceuticals, Sulfadiazine (SDZ) is widely used in animal husbandry. Its residues were detected in different environmental compartments. However, soil is a hot spot for SDZ as it receives a large portion of excreted compounds through the application of manure during soil fertilization. Ample studies on the fate of SDZ in soils showed that a large portion forms nonextractable residues (NER) along with transformation products and a low mineralization (Mueller et al., 2013). A common observation was an initially fast formation of NER up to 10% of the applied amount promptly after the application of SDZ to soil, and this portion increased up to 50% within a few days (Mueller et al., 2013; Nowak et al., 2011). A common finding for SDZ, as for other sulfonamides, was biphasic kinetics of the formation of NER, which was attributed to the occurrence of two reaction processes: a rapid, often reversible process and a slower, irreversible process (Weber et al., 1996). A single-phase reaction process was also established under anaerobic treatment (Gulkowska et al., 2014). A major focus of this work is to elucidate a reaction mechanism of covalent binding of SDZ to soil that is currently required to estimate a risk of NER formed by SDZ in soils for human health. Taking into account a key role of the amine functional groups of SDZ on its reactivity in soil, nitroxide radicals with the sewed aromatic or aliphatic amines labeled soil samples and then, were investigated by means of ESR spectroscopy. 2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-yloxy and 4-amino-2,2,6,6-Tetramethylpiperidin-1-oxyl modeled decomposition products of SDZ with the aromatic and aliphatic amines, respectively. The application of the defined combination of both spin labels (SL) to different soils well simulated a change of a paramagnetic signal of soil organic radicals interacted with SDZ. After their application to soil, SL were found in soil sites characterized

  20. Spectroscopic Evidence for Covalent Binding of Sulfadiazine to Natural Soils via 1,4-nucleophilic addition (Michael Type Addition) studied by Spin Labeling ESR

    NASA Astrophysics Data System (ADS)

    Aleksandrova, Olga

    2015-04-01

    Among different classes of veterinary pharmaceuticals, Sulfadiazine (SDZ) is widely used in animal husbandry. Its residues were detected in different environmental compartments. However, soil is a hot spot for SDZ as it receives a large portion of excreted compounds through the application of manure during soil fertilization. Ample studies on the fate of SDZ in soils showed that a large portion forms nonextractable residues (NER) along with transformation products and a low mineralization (Mueller et al., 2013). A common observation was an initially fast formation of NER up to 10% of the applied amount promptly after the application of SDZ to soil, and this portion increased up to 50% within a few days (Mueller et al., 2013; Nowak et al., 2011). A common finding for SDZ, as for other sulfonamides, was biphasic kinetics of the formation of NER, which was attributed to the occurrence of two reaction processes: a rapid, often reversible process and a slower, irreversible process (Weber et al., 1996). A single-phase reaction process was also established under anaerobic treatment (Gulkowska et al., 2014). A major focus of this work is to elucidate a reaction mechanism of covalent binding of SDZ to soil that is currently required to estimate a risk of NER formed by SDZ in soils for human health. Taking into account a key role of the amine functional groups of SDZ on its reactivity in soil, nitroxide radicals with the sewed aromatic or aliphatic amines labeled soil samples and then, were investigated by means of ESR spectroscopy. 2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-yloxy and 4-amino-2,2,6,6-Tetramethylpiperidin-1-oxyl modeled decomposition products of SDZ with the aromatic and aliphatic amines, respectively. The application of the defined combination of both spin labels (SL) to different soils well simulated a change of a paramagnetic signal of soil organic radicals interacted with SDZ. After their application to soil, SL were found in soil sites characterized

  1. Paramagnetic metal ions in pulsed ESR distance distribution measurements.

    PubMed

    Ji, Ming; Ruthstein, Sharon; Saxena, Sunil

    2014-02-18

    The use of pulsed electron spin resonance (ESR) to measure interspin distance distributions has advanced biophysical research. The three major techniques that use pulsed ESR are relaxation rate based distance measurements, double quantum coherence (DQC), and double electron electron resonance (DEER). Among these methods, the DEER technique has become particularly popular largely because it is easy to implement on commercial instruments and because programs are available to analyze experimental data. Researchers have widely used DEER to measure the structure and conformational dynamics of molecules labeled with the methanethiosulfonate spin label (MTSSL). Recently, researchers have exploited endogenously bound paramagnetic metal ions as spin probes as a way to determine structural constraints in metalloproteins. In this context Cu(2+) has served as a useful paramagnetic metal probe at X-band for DEER based distance measurements. Sample preparation is simple, and a coordinated-Cu(2+) ion offers limited spatial flexibility, making it an attractive probe for DEER experiments. On the other hand, Cu(2+) has a broad absorption ESR spectrum at low temperature, which leads to two potential complications. First, the Cu(2+)-based DEER time domain data has lower signal to noise ratio compared with MTSSL. Second, accurate distance distribution analysis often requires high-quality experimental data at different external magnetic fields or with different frequency offsets. In this Account, we summarize characteristics of Cu(2+)-based DEER distance distribution measurements and data analysis methods. We highlight a novel application of such measurements in a protein-DNA complex to identify the metal ion binding site and to elucidate its chemical mechanism of function. We also survey the progress of research on other metal ions in high frequency DEER experiments. PMID:24289139

  2. Persistent free radical ESR signals in marine bivalve tissues

    SciTech Connect

    Mehlorn, R.J.; Mendez, A.T.; Higashi, R.; Fan, T.

    1992-08-01

    Freeze-dried homogenates of the oyster Crassostrea rhizophorae collected from waters in Puerto Rico near urban and industrial sites as well as at relatively pristine locations yielded electron spin resonance (ESR) spectra characteristic of free radicals as well as spectral components of transition metal ions, dominated by manganese. The magnitudes of these ESR signals and the concentrations of trace elements (determined by X-ray fluorescence) varied considerably among oyster samples, masking any potential correlation with polluted waters. Laboratory studies were initiated to identify the factors controlling the magnitudes of the tissue free radical ESR signals. Another mollusc, Mytilus californianus collected at the Bodega Marine laboratory in northern California, was fractionated into goneds and remaining tissue. Freeze-dried homogenates of both fractions exhibited ESR signals that increased gradually with time. ESR signals were observed in freeze-dried perchloric acid (PCA) precipitates of the homogenates, delipidated PCA precipitates, and in chloroform extracts of these precipitates. Acid hydrolysis to degrade proteins to amino acids produced a residue, which yielded much larger ESR free radical signals after freeze-drying. Freshly thawed homogenates of Crassostrea rhizophorae also exhibited ESR signals. A laboratory model of copper stress in Crassostrea rhizophorae was developed to study the effect of this transition metal on dssue free radicals. Preliminary results suggested that sublethal copper exposure had little effect on tissue fire radicals, except possibly for a signal enhancement in an oyster fraction that was enriched in kidney granules. Since kidney granules are known to accumulate heavy metals in mussels and probably other marine bivalves, this signal enhancement may prove to be an indicator of free radical processes associated with heavy metal deposition in molluscs.

  3. Neon and argon matrix ESR and theoretical studies of the 12CH3Cd, 12CD3Cd, 13CH3Cd, 12CH3111Cd, and 12CH3113Cd radicals

    NASA Astrophysics Data System (ADS)

    Karakyriakos, Emmanuel; Davis, Jeffrey R.; Wilson, Carl J.; Yates, Sally A.; McKinley, Allan J.; Knight, Lon B.; Babb, Robert; Tyler, D. J.

    1999-02-01

    Electron spin resonance (ESR) studies are reported for the first time on the various isotopomers of the CH3Cd radical isolated in neon and argon matrices. The radicals were generated in neon matrices by the reaction of laser-ablated cadmium metal and various methyl precursors, and in argon matrices by x-irradiation. The neon matrix values measured were g⊥=1.9491(1), A⊥(H)=17.0(1) MHz, A⊥(D)=2.6(1) MHz, A⊥(13C)=163(3) MHz, and A⊥(111Cd)=-3083(3) MHz, and estimates were derived for A∥(13C)=230(50) MHz and A∥(111Cd)=-3486(5) MHz. The argon matrix values measured were g⊥=1.952(1), A⊥(H)=16(1) MHz and A⊥(111Cd)=-3301(3) MHz, and an estimate was derived for A∥(111Cd)=-3704(5) MHz. The ESR experimental Adip(111Cd) values for the neon and the argon matrices agree with the reported gas-phase value [J. Chem. Phys. 101, 6396 (1994)]. The matrix ESR Aiso(111Cd) values show small shifts compared with the gas-phase results (5% greater for the neon matrix and 12% greater for the argon matrix). At 4.3 K in the neon matrices, additional ESR lines assigned to tunneling phenomena were observed. The radical geometry obtained from ab initio calculations was consistent with that reported from the various experimental results. Multireference single and double excitation configuration interaction (MRSDCI) calculations of the hyperfine interactions gave values that were consistently below the experimental values of Aiso and Adip for 111Cd, H, and 13C. MRSDCI calculations for the CdH radical showed an analogous trend.

  4. ESR dating of teeth from Brazilian megafauna

    NASA Astrophysics Data System (ADS)

    Oliveira, L. C.; Kinoshita, A.; Barreto, A. M. F.; Figueiredo, A. M.; Silva, J. L. L.; Baffa, O.

    2010-11-01

    The study of radiation defects created in biomaterials, such as bone and teeth, can be used in dating with importance to palaeontology and archaeology. Two Stegomastodon teeth (AL1 and AL2) from north-eastern Brazilian megafauna were studied by electron spin resonance (ESR) spectroscopy. The samples were collected in Fazenda Ovo da Ema, (913349 / 3714965) UTM, Alagoas state, Brazil. The dating of these samples can contribute to the better knowledge of megafauna presence in this region as well as to the events associated to the extinction of these species.

  5. Synthesis, spectroscopic, anticancer and antibacterial studies of Ni(II) and Cu(II) complexes with 2-carboxybenzaldehyde thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Vandana

    2014-08-01

    Ni(II) and Cu(II) complexes of 2-carboxybenzaldehyde thiosemicarbazone (L) were synthesized and investigated by their spectral and analytical data. These newly synthesized complexes have a composition of M(L)X(H2O)2 (where M = Ni(II), Cu(II) and X = Cl-, NO3-, CH3COO-) and (L) is the tridentate Schiff base ligand. The ligand and its complexes have been characterized on the basis of analytical, molar conductivity, magnetic susceptibility measurements, FT-IR, ESR, 1H NMR and electronic spectral analysis. All the compounds were non-electrolytic in nature. On the basis of spectral studies an octahedral geometry has been assigned for Ni(II) and a tetragonal geometry for Cu(II) complexes. The ligand and its metal complexes were screened for their anticancer studies against human breast cancer cell lines MCF-7 and calculated minimum inhibitory concentration and also for antibacterial activity using Kirby-Bauer single disk susceptibility test.

  6. Synthesis, spectroscopic, anticancer and antibacterial studies of Ni(II) and Cu(II) complexes with 2-carboxybenzaldehyde thiosemicarbazone.

    PubMed

    Chandra, Sulekh; Vandana

    2014-08-14

    Ni(II) and Cu(II) complexes of 2-carboxybenzaldehyde thiosemicarbazone (L) were synthesized and investigated by their spectral and analytical data. These newly synthesized complexes have a composition of M(L)X(H2O)2 (where M=Ni(II), Cu(II) and X=Cl(-), NO3(-), CH3COO(-)) and (L) is the tridentate Schiff base ligand. The ligand and its complexes have been characterized on the basis of analytical, molar conductivity, magnetic susceptibility measurements, FT-IR, ESR, (1)H NMR and electronic spectral analysis. All the compounds were non-electrolytic in nature. On the basis of spectral studies an octahedral geometry has been assigned for Ni(II) and a tetragonal geometry for Cu(II) complexes. The ligand and its metal complexes were screened for their anticancer studies against human breast cancer cell lines MCF-7 and calculated minimum inhibitory concentration and also for antibacterial activity using Kirby-Bauer single disk susceptibility test. PMID:24747857

  7. Reduction process of nitroxyl spin probes used in Overhauser-enhanced magnetic resonance imaging: An ESR study

    NASA Astrophysics Data System (ADS)

    Meenakumari, V.; Jawahar, A.; Premkumar, S.; Benial, A. Milton Franklin

    2016-05-01

    The Electron spin resonance studies on the reduction process of nitroxyl spin probes were carried out for 1mM 14N- labeled nitroxyl radicals in pure water and 1 mM concentration of ascorbic acid as a function of time. The electron spin resonance parameters, such as line width, hyperfine coupling constant, g-factor, signal intensity ratio and rotational correlation time were estimated. The 3-carbamoyl-PROXYL radical has narrowest line width and fast tumbling motion compared with 3-carboxy-PROXYL, 4-methoxy-TEMPO, and 4-acetamido-TEMPO radicals. The half life time and decay rate were estimated for 1mM concentration of 14N- labeled nitroxyl radicals in 1 mM concentration of ascorbic acid. From the results, the 3-carbamoyl-PROXYL has long half life time and high stability compared with 3-carboxy-PROXYL, 4-methoxy-TEMPO and 4-acetamido-TEMPO radicals. Therefore, this study reveals that the 3-carbamoyl-PROXYL radical can act as a good redox sensitive spin probe for Overhauser-enhanced Magnetic Resonance Imaging.

  8. Studies on spin-trapped radicals in. gamma. -irradiated aqueous L-valine solutions by high-performance liquid chromatography and ESR spectroscopy

    SciTech Connect

    Makino, K.

    1980-05-01

    Short-lived radicals produced in ..gamma..-irradiated aqueous L-valine solution were investigated by the method of spin trapping and subsequently by means of high-performance liquid chromatography combined with ESR spectroscopy. Four spin adducts due to L-valine could be identified. Among them, even the diastereoisomeric spin adducts due to L-valine could be separated. In addition, the effect of pH on the change in the spectra of the diastereoisomers is discussed.

  9. Submillimeter Wave ESR Study of Magnetic Excitations in the Ising Ferromagnetic Chain CoNb 2O 6

    NASA Astrophysics Data System (ADS)

    Kunimoto, Takashi; Nagasaka, Keigo; Nojiri, Hiroyuki; Luther, Sebastian; Motokawa, Mitsuhiro; Ohta, Hitoshi; Goto, Tomohiro; Okubo, Susumu; Kohn, Kay

    1999-05-01

    Magnetic excitations in the Ising ferromagnetic chain CoNb2O6 have been studied by submillimeter wave electron spin resonance in strong transverse magnetic fields. A distinct non-linear field dependence of the resonance branches and also zero field splittings have been observed. A large residual intensity of the spin-cluster resonance was found which was caused by the strong mixing among the different n-fold spin-clusters. In addition to a series of n-fold spin-cluster excitations, we also discovered a new set of spin-cluster excitation which can be attributed to non-integer n such as n˜1.5 or n˜2.5 for the first time. This effect is explained by the change of the quantization axis of the system in strong transverse magnetic fields. These new aspects of spin-cluster excitation show the significant effect of transverse magnetic fields on the magnetic excitation in an Ising ferromagnetic chain.

  10. Limited Immersion in Cued Speech: A Case Study.

    ERIC Educational Resources Information Center

    Gordon, Malcolm; And Others

    The case study examines the effects on the receptive and expressive English language of a deaf 14 year old after a period of limited language immersion using Cued Speech, in which every sound in a word is represented both expressively and receptively. In a four week period the S spent approximately 14 hours per week with a modeler who cued speech…

  11. Applications of ESR to carbonaceous materials

    SciTech Connect

    Singer, L.S.; Lewis, I.C.

    1982-01-01

    The applicatioins of electron spin resonance (ESR) to carbonaceous materials are reviewed. The stable paramagnetic species observed in the products of low-temperature pyrolyis are odd-alternate neutral free radicals, whereas the unpaired spins of higher temperature carbons and graphites are primarily conduction electrons. The variety of ESR properties and phenomena requires special attention to techniques of measurement and interpretations of results. The relevance to the carbonization process of the free radicals observed by ESR is also discussed.

  12. Effect of Base Stacking on the Acid-Base Properties of the Adenine Cation Radical [A•+] in Solution: ESR and DFT Studies

    PubMed Central

    Adhikary, Amitava; Kumar, Anil; Khanduri, Deepti

    2015-01-01

    In this study, the acid–base properties of the adenine cation radical are investigated by means of experiment and theory. Adenine cation radical (A•+) is produced by one-electron oxidation of dAdo and of the stacked DNA-oligomer (dA)6 by Cl2•− in aqueous glass (7.5 M LiCl in H2O and in D2O) and investigated by ESR spectroscopy. Theoretical calculations and deuterium substitution at C8–H and N6–H in dAdo aid in our assignments of structure. We find the pKa value of A•+ in this system to be ca. 8 at 150 K in seeming contradiction to the accepted value of ≤ 1 at ambient temperature. However, upon thermal annealing to ≥160 K, complete deprotonation of A•+ occurs in dAdo in these glassy systems even at pH ca. 3. A•+ found in (dA)6 at 150 K also deprotonates on thermal annealing. The stability of A•+ at 150 K in these systems is attributed to charge delocalization between stacked bases. Theoretical calculations at various levels (DFT B3LYP/6-31G*, MPWB95, and HF-MP2) predict binding energies for the adenine stacked dimer cation radical of 12 to 16 kcal/mol. Further DFT B3LYP/6-31G* calculations predict that, in aqueous solution, monomeric A•+ should deprotonate spontaneously (a predicted pKa of ca. −0.3 for A•+). However, the charge resonance stabilized dimer AA•+ is predicted to result in a significant barrier to deprotonation and a calculated pKa of ca. 7 for the AA•+ dimer which is 7 pH units higher than the monomer. These theoretical and experimental results suggest that A•+ isolated in solution and A•+ in adenine stacks have highly differing acid–base properties resulting from the stabilization induced by hole delocalization within adenine stacks. PMID:18611019

  13. ESR

    MedlinePlus

    ... due to: Anemia Cancers such as lymphoma or multiple myeloma Kidney disease Pregnancy Thyroid disease The immune system ... Heart failure - overview Hypersensitivity vasculitis Macroglobulinemia of Waldenstrom Multiple ... vasculitis Polycythemia - newborn Polycythemia vera Polymyalgia ...

  14. Electronic structures of CuTPP and CuTPP(F) complexes. A combined experimental and theoretical study I.

    PubMed

    Mangione, Giulia; Carlotto, Silvia; Sambi, Mauro; Ligorio, Giovanni; Timpel, Melanie; Vittadini, Andrea; Nardi, Marco Vittorio; Casarin, Maurizio

    2016-07-28

    Copper complexes of tetraphenylporphyrin (H2TPP) and tetrakis(pentafluorophenyl)porphyrin (H2TPP(F)) deposited as thin films on Au(111) have been studied experimentally and theoretically. Core level emissions from C 1s, N 1s, F 1s and Cu 2p as well as valence states of CuTPP and CuTPP(F) have been investigated using surface photoelectron spectroscopy. The interpretation of experimental results has been guided by theoretical calculations carried out on isolated species in the habit of the density functional theory. Reference to experimental and theoretical outcomes pertaining to H2TPP and H2TPP(F) allowed a confident and detailed assignment of the title molecules' X-ray and ultraviolet photoemission data. With specific reference to the latter, similar to copper phthalocyanine (CuPc), whose coordinative pocket mirrors the CuTPP/CuTPP(F) ones, the lowest ionization energy of the title compounds implies electron ejection from a ring orbital rather than from the Cu 3d-based singly occupied molecular orbital. Moreover, analogous to CuPc, the ionic contribution appears to play an important role in the Cu-N bonding. Nevertheless, differences in the number, symmetry, nature and relative position of CuTPP/CuTPP(F) occupied frontier orbitals compared to CuPc may be stated only by considering in great detail the Cu-ligand covalent interactions. PMID:27166746

  15. Provenance study of obsidians from the archaeological site of La Maná (Ecuador) by electron spin resonance (ESR), SQUID magnetometry and 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Duttine, M.; Scorzelli, R. B.; Poupeau, G.; Bustamante, A.; Bellido, A. V.; Lattini, R. M.; Guillaume-Gentil, N.

    2007-02-01

    Obsidians from major Ecuadorian sources (outcrops) were analyzed by electron spin resonance, SQUID magnetometry and 57Fe Mössbauer spectroscopy. If the last technique allows to discriminate obsidians from the Quiscatola source, an association of ESR with SQUID magnetometry permits to differentiate obsidians from the sources of Cotopaxi volcano, from the Quiscatola and Mullumica-Callejones sources of the Chacana caldera and to infer that the 12 analyzed obsidians from the pre-Hispanic site of La Maná come from the Mullumica-Callejones source.

  16. High static pressure alters water-pool properties in reversed micelles formed by aerosol OT (sodium bis(2-ethylhexyl)sulfosuccinate): A high pressure ESR study

    NASA Astrophysics Data System (ADS)

    Sueishi, Yoshimi; Yoshioka, Daisuke; Negi, Mieko; Kotake, Yashige

    2005-11-01

    ESR spectra of Fremy's salt in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reversed micelles were recorded at high pressures in order to monitor dynamic properties of water molecules inside water pools. Rotational correlation times of Fremy's salt in large AOT water pools slightly decreased with increasing pressure, conversely those in small water pools increased with pressure: Δ V‡ for the rotational motion = -1.05 and 9.19 cm 3 mol -1 at ω0 = 20 and 2, respectively. These results demonstrate that most water molecules in small water pools are bound to AOT head groups and show very different physical properties from bulk water.

  17. Ferromagnetism studies of Cu-doped and (Cu, Al) co-doped ZnO thin films

    NASA Astrophysics Data System (ADS)

    Wu, S. Z.; Yang, H. L.; Xu, X. G.; Miao, J.; Jiang, Y.

    2011-01-01

    We have studied the room temperature ferromagnetism (FM) in Cu-doped and (Cu, Al) co-doped ZnO thin films which were grown on quartz substrates by chemical method based on a sol-gel process combining with spin-coating technology. X-ray diffraction (XRD) patterns demonstrate that both the Cu-doped and (Cu, Al) co-doped ZnO films have the hexagonal wurtzite structure with c-axis orientation. Alternating Gradient Magnetometer (AGM) measurements confirm that all the doped ZnO samples are ferromagnetic at room temperature. When the doped Cu content is 1 %, the Cu-doped ZnO film has the strongest FM. The FM significantly decreases in the (Cu, Al) co-doped ZnO films. The doping of Al ions suppresses the FM induced by the doped Cu ions.

  18. The Evaluation of IL6 and ESR1 Gene Polymorphisms in Primary Dysmenorrhea.

    PubMed

    Ozsoy, Asker Zeki; Karakus, Nevin; Yigit, Serbulent; Cakmak, Bulent; Nacar, Mehmet Can; Yılmaz Dogru, Hatice

    2016-01-01

    Primary dysmenorrhea is the most common gynecological complaint with painful menstrual cramps in pelvis without any pathology. It affects about half of menstruating women, and it causes significant disruption in quality of life. We investigated the association between IL6 gene promoter and ESR1 gene XbaI and PvuII polymorphisms and primary dysmenorrhea. In this case-control study, 152 unrelated young women with primary dysmenorrhea and 150 unrelated healthy age-matched controls participated. Genomic DNA was isolated and IL6 and ESR1 gene polymorphisms were genotyped using PCR-based RFLP assay. The distribution of genotype and allele frequencies of IL6 gene promoter and ESR1 gene XbaI polymorphisms were not statistically different between patients and controls (p > 0.05). However, the genotype and allele frequencies of ESR1 gene PvuII polymorphism showed statistically significant differences between primary dysmenorrhea patients and controls (p = 0.009 and p = 0.021, respectively). Statistically significant associations were also observed between age and married status of primary dysmenorrhea patients and ESR1 gene PvuII polymorphism (p = 0.044 and p = 0.023, respectively). In combined genotype analyses, AG at ESR1 XbaI and TC at ESR1 PvuII loci encoded a p-value of 0.027. Thus, individuals who are heterozygote at both loci have a lower risk of developing primary dysmenorrhea. Our study suggests no strong association between IL6 gene promoter and ESR1 gene XbaI polymorphisms and primary dysmenorrhea in Turkish women. However, ESR1 gene PvuII polymorphism showed statistically significant differences between primary dysmenorrhea patients and controls. The potential association between ESR1 gene PvuII polymorphism and age and married status of dysmenorrhea patients deserves further consideration. PMID:26700208

  19. In situ TEM Studies of the Initial Oxidation stage of Cu and Cu Alloy Thin Films

    NASA Astrophysics Data System (ADS)

    Yang, Judith; Kang, Yihong; Luo, Langli; Ciston, James; Stach, Eric; Zhou, Guangwen

    2012-02-01

    The fundamental understanding of oxidation at the nanoscale is important for the environmental stability of coating materials as well as processing of oxide nanostructures. Our previous studies show the epitaxial growth of Cu2O islands during the initial stages of oxidation of Cu thin films, where surface diffusion and strain impact the oxide development and morphologies. The addition of secondary elements changes the oxidation mechanism. If the secondary element is non-oxidizing, such as Au, it will limit the Cu2O island growth due to the depletion of Cu near the oxide islands. When the secondary element is oxidizing, for example Ni, the alloy will show more complex behaviour, where duplex oxide islands were observed. Nucleation density and growth rate of oxide islands are observed under various temperatures and oxygen partial pressures (pO2) as a function of time by in situ ultra high vacuum (UHV)-transmission electron microscopy (TEM). Our initial results of Cu-Ni(001) oxidation is that the oxide epitaxy and morphologies change as function of Ni concentration. For higher spatial resolution, we are examining the atomic scale oxidation by aberration-corrected ETEM with 1å resolution.

  20. The role of copper species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction

    NASA Astrophysics Data System (ADS)

    Liang, Chunxia; Li, Xinyong; Qu, Zhenping; Tade, Moses; Liu, Shaomin

    2012-02-01

    UV-vis spectra, XRD, H2-TPR, TEM and ESR were used to characterize a series of Cu/γ-Al2O3 catalysts, which were prepared by incipient wetness impregnation using copper nitrate, copper acetate or copper sulfate as precursors, to study the role of Cu species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction. It was found that the mixture of CuO phase and CuAl2O4 phase formed on various Cu/γ-Al2O3 catalysts, and the Cu species and dispersion had significant influence on the Cu/γ-Al2O3 activity. Highly dispersed CuO phase on the support would be related with its high activity for the NH3-SCO reaction.

  1. ESR technique for noninvasive way to quantify cyclodextrins effect on cell membranes

    SciTech Connect

    Grammenos, A.; Mouithys-Mickalad, A.; Guelluy, P.H.; Lismont, M.; Piel, G.; Hoebeke, M.

    2010-07-30

    Research highlights: {yields} ESR: a new tool for cyclodextrins study on living cells. {yields} Cholesterol and phospholipid extraction by Rameb in a dose- and time-dependent way. {yields} Extracted phospholipids and cholesterol form stable aggregates. {yields} ESR spectra show that lipid rafts are damaged by Rameb. {yields} Quantification of the cholesterol extraction on cell membranes in a noninvasive way. -- Abstract: A new way to study the action of cyclodextrin was developed to quantify the damage caused on cell membrane and lipid bilayer. The Electron Spin Resonance (ESR) spectroscopy was used to study the action of Randomly methylated-beta-cyclodextrin (Rameb) on living cells (HCT-116). The relative anisotropy observed in ESR spectrum of nitroxide spin probe (5-DSA and cholestane) is directly related to the rotational mobility of the probe, which can be further correlated with the microviscosity. The use of ESR probes clearly shows a close correlation between cholesterol contained in cells and cellular membrane microviscosity. This study also demonstrates the Rameb ability to extract cholesterol and phospholipids in time- and dose-dependent ways. In addition, ESR spectra enabled to establish that cholesterol is extracted from lipid rafts to form stable aggregates. The present work supports that ESR is an easy, reproducible and noninvasive technique to study the effect of cyclodextrins on cell membranes.

  2. History of the youngest members of the Valles Rhyolite, Valles caldera, New Mexico using ESR dating method

    SciTech Connect

    Ogoh, K; Toyoda, S; Ikeda, S; Ikeya, M; Goff, F

    1991-01-01

    The cooling history of the Valles caldera was studied by the electron spin resonance (ESR) dating method using Al and Ti centers in quartz grains which were separated from the youngest units of the Valles Rhyolite. The ESR apparent ages are much younger than fission track ages and {sup 39}Ar- {sup 40}Ar ages. Three possibilities are suggested, the first is that the ESR ages are real, the second is that ESR method did not work for these samples, and the third is that about 10--40 ka, the signal intensity was partially reduced by a thermal event such as proposed by Harrison et al. (1986). Research on the first and second possibilities is continuing. The third possibility might explain the difference between ESR ages and those by other methods (fission track and {sup 39}Ar- {sup 40}Ar). ESR dating has produced new insights regarding the history of the Valles caldera.

  3. ESR in CVD silicon and silicon-carbon alloys

    NASA Astrophysics Data System (ADS)

    Gaczi, P. J.; Booth, D. C.

    1981-03-01

    Electron spin resonance (ESR) is reported in three groups of chemical vapor deposited silicon films. It is noted that group I films are amorphous Si(x)C(100-x) alloys prepared from silane and acetylene at a substrate temperature of 630 C that have a spin density of 3 x 10 to the 19th/cu cm. The silicon-carbon films have been developed as structurally stable selective absorbers for photothermal solar energy conversion. Group II films are nonalloyed amorphous silicon films prepared below 660 C that have a spin density of 1 x 10 to the 19th, while group III films are polycrystalline films prepared above 670 C with a density of 0.5 x 10 to the 19th/cu cm. The exchange interaction between spins is sufficiently strong in the group I silicon-carbon alloys so that an average g value is observed and no evidence of superposition is found in agreement with the amorphous Si-Ge results of Kumeda et al. (1977). ESR saturation and line broadening as a function of microwave power in samples representative of the three groups is observed. A trend, in the order group III, II, I, is found of increasing spin system homogeneity, indicating that the exchange coupled spin clusters contain increasing numbers of spins.

  4. Adenine adlayers on Cu(111): XPS and NEXAFS study.

    PubMed

    Tsud, Nataliya; Bercha, Sofiia; Ševčíková, Klára; Acres, Robert G; Prince, Kevin C; Matolín, Vladimír

    2015-11-01

    The adsorption of adenine on Cu(111) was studied by photoelectron and near edge x-ray absorption fine structure spectroscopy. Disordered molecular films were deposited by means of physical vapor deposition on the substrate at room temperature. Adenine chemisorbs on the Cu(111) surface with strong rehybridization of the molecular orbitals and the Cu 3d states. Annealing at 150 °C caused the desorption of weakly bonded molecules accompanied by formation of a short-range ordered molecular adlayer. The interface is characterized by the formation of new states in the valence band at 1.5, 7, and 9 eV. The present work complements and refines existing knowledge of adenine interaction with this surface. The coverage is not the main parameter that defines the adenine geometry and adsorption properties on Cu(111). Excess thermal energy can further rearrange the molecular adlayer and, independent of the initial coverage, the flat lying stable molecular adlayer is formed. PMID:26547179

  5. Adenine adlayers on Cu(111): XPS and NEXAFS study

    SciTech Connect

    Tsud, Nataliya; Bercha, Sofiia; Ševčíková, Klára; Matolín, Vladimír; Acres, Robert G.; Prince, Kevin C.

    2015-11-07

    The adsorption of adenine on Cu(111) was studied by photoelectron and near edge x-ray absorption fine structure spectroscopy. Disordered molecular films were deposited by means of physical vapor deposition on the substrate at room temperature. Adenine chemisorbs on the Cu(111) surface with strong rehybridization of the molecular orbitals and the Cu 3d states. Annealing at 150 °C caused the desorption of weakly bonded molecules accompanied by formation of a short-range ordered molecular adlayer. The interface is characterized by the formation of new states in the valence band at 1.5, 7, and 9 eV. The present work complements and refines existing knowledge of adenine interaction with this surface. The coverage is not the main parameter that defines the adenine geometry and adsorption properties on Cu(111). Excess thermal energy can further rearrange the molecular adlayer and, independent of the initial coverage, the flat lying stable molecular adlayer is formed.

  6. Study of thermal stability of Cu2Se thermoelectric material

    NASA Astrophysics Data System (ADS)

    Bohra, Anil; Bhatt, Ranu; Bhattacharya, Shovit; Basu, Ranita; Ahmad, Sajid; Singh, Ajay; Aswal, D. K.; Gupta, S. K.

    2016-05-01

    Sustainability of thermoelectric parameter in operating temperature range is a key consideration factor for fabricating thermoelectric generator or cooler. In present work, we have studied the stability of thermoelectric parameter of Cu2Se within the temperature range of 50-800°C. Temperature dependent Seebeck coefficients and electrical resistivity measurement are performed under three continuous thermal cycles. X-ray diffraction pattern shows the presence of mixed cubic-monoclinic Cu2Se phase in bare pellet which transforms to pure α-Cu2Se phase with repeating thermal cycle. Significant enhancement in Seebeck coefficient and electrical resistivity is observed which may be attributed to (i) Se loss observed in EDS and (ii) the phase transformation from mixed cubic-monoclinic structure to pure monoclinic α-Cu2Se phase.

  7. DNA CLEAVAGE AND DETECTION OF DNA RADICALS FORMED FROM HYDRALAZINE AND COPPER (II) BY ESR AND IMMUNO-SPIN TRAPPING

    PubMed Central

    Sinha, Birandra K.; Leinisch, Fabian; Bhattacharjee, Suchandra; Mason, Ronald P.

    2014-01-01

    Metal ion-catalyzed oxidation of hydrazine and its derivatives leads to the formation of the hydrazyl radical and subsequently to oxy-radicals in the presence of molecular oxygen. Here we have examined the role of Cu2+-catalyzed oxidation of hydralazine in the induction of DNA damage. Neither 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) nor dimethyl sulfoxide (DMSO) were effective in inhibiting hydralazine-Cu2+-induced DNA damage. Singlet oxygen did not appear to participate in this DNA cleavage. The one-electron oxidation of hydralazine also leads to the formation of DNA radicals as confirmed by immuno-spin trapping with 5, 5-dimethyl-1-pyrroline-N-oxide. Electron spin resonance (ESR) and spin trapping studies further confirmed the formation of DNA radicals; predominantly 2′-deoxyadenosine radical adducts were detected, while some radicals were also detected with other nucleosides. Our results suggest that free hydroxyl radicals may not be the main damaging species causing DNA cleavage, and possibly, Cu-peroxide complexes, formed from Cu+-H2O2, areresponsible for this hydralazine-Cu2+-induced DNA cleavage. PMID:24502259

  8. ESR studies of the spin dynamics in quasi-one-dimensional iodo-bridged diplatinum complex Pt2(n-pentylCS2)4I

    NASA Astrophysics Data System (ADS)

    Tanaka, Hisaaki; Kuroda, Shin-Ichi; Yamashita, Takami; Mitsumi, Minoru; Toriumi, Koshiro

    2006-06-01

    ESR measurements have been performed on a quasi-one-dimensional (Q1D) halogen-bridged binuclear metal-complex Pt2(n-pentylCS2)4I which exhibits successive electronic phase transitions. Anisotropy of the ESR linewidth shows a drastic change around 215K where the phase transition takes place between a nonmagnetic alternate-charge-polarization (ACP) state for low temperatures and a paramagnetic averaged-valence (AV) state with a relatively good electrical conductivity for higher temperatures. In the AV state, a clear minimum of the linewidth is observed around 50° from the chain direction due to the contribution of the secular 1D dipolar term varying as 3cos2θ-1 , where θ denotes the angle between the external magnetic field and the chain axis. In addition to the dipolar contribution, the linewidth also exhibits temperature-dependent spin-phonon contribution. These features of linewidths are consistent with those reported previously for Q1D conductors such as charge transfer salts and Pt-complexes, providing microscopic evidence for the occurrence of a Q1D conduction-electron system in the present bimetal complex. In the ACP state, the spin concentration drastically decreases due to the nonmagnetic nature of the background electronic state. The linewidth shows a uniaxial anisotropy with respect to the chain axis, which can be reasonably ascribed to the anisotropy of unresolved hyperfine structures due to Pt and iodine nuclear spins. The spin susceptibility shows a clear enhancement from Curie-type behavior, accompanied with a change of the line shape from a nearly Gaussian at 4K to Lorentzian with motional narrowing as the temperature is raised. The results further support our previous conjecture that the observed spins are thermally excited solitons.

  9. The occurrence of free radicals in milled and irradiated paprika as detected by ESR

    NASA Astrophysics Data System (ADS)

    Kispéter, J.; Horváth, L. J.; Szabó, I.

    1999-08-01

    Ionising radiation and various other types of treatment can induce oxidising processes that give rise to free radicals in materials. This paper reports an ESR study of free radicals in spicy paprika in various phases of grinding and in samples of different particle sizes as functions of the absorbed gamma dose and storage time. In 7th phase of grinding, the ESR intensity first increased and then decreased after conditioning. The ESR intensity increased with increase in the absorbed dose, and then decreased during the 8 weeks of storage. This declining intensity demonstrates the simultaneous presence of free radicals having short and long shelf life in paprika samples.

  10. Synthesis, characterization, in vitro antimicrobial and DNA cleavage studies of Co(II), Ni(II) and Cu(II) complexes with ONOO donor coumarin Schiff bases

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Unki, Shrishila N.; Kulkarni, Ajaykumar D.; Naik, Vinod H.; Badami, Prema S.

    2011-01-01

    A series of Co(II), Ni(II) and Cu(II) complexes have been synthesized with Schiff bases derived from 2-hydroxy-1-naphthaldehyde and 2-oxo-2H-chromene-3-carbohydrazide/6-bromo-2-oxo-2H-chromene-3-carbohydrazide. The chelation of the complexes has been proposed in the light of analytical, spectral (IR, UV-Vis, 1H NMR, ESR, FAB-mass and fluorescence), magnetic and thermal studies. The measured molar conductance values indicate that, the complexes are non-electrolytic in nature. The redox behavior of the complexes was investigated with electrochemical method by using cyclic voltammetry. The Schiff bases and their metal complexes have been screened for their in vitro antibacterial ( Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Salmonella typhi) and antifungal activities ( Candida albicans, Cladosporium and Aspergillus niger) by MIC method. The DNA cleavage is studied by agarose gel electrophoresis method.

  11. Novel copper (Cu) loaded core-shell silica nanoparticles with improved Cu bioavailability: synthesis, characterization and study of antibacterial properties.

    PubMed

    Maniprasad, Pavithra; Santra, Swadeshmukul

    2012-08-01

    We report synthesis of a novel core-shell silica based antimicrobial nanoparticles where the silica shell has been engineered to accommodate copper (Cu). Synthesis of the core-shell Cu-silica nanoparticle (C-S CuSiO2NP) involves preparation of base-hydrolyzed Stöber silica "seed" particles first, followed by the acid-catalyzed seeded growth of the Cu-silica shell layer around the core. The Scanning Electron Microscopy (SEM) and the Transmission Electron Microscopy (TEM) measured the seed particle size to be -380 nm and the shell thickness to be -35 nm. The SEM particle characterization confirms formation of highly monodispersed particles with smooth surface morphology. Characterization of particle size distribution in solution by Dynamic Light Scattering (DLS) technique was fairly consistent with the electron microscopy results. Loading of Cu to nanoparticles was confirmed by the SEM-Energy Dispersive X-Ray Spectroscopy (EDS) and Atomic Absorption Spectroscopy (AAS). The Cu loading was estimated to be 0.098 microg of metallic copper per mg of C-S CuSiO2NP material by the AAS technique. Antibacterial efficacy of C-S CuSiO2NP was evaluated against E. coli and B. subtilis using Cu hydroxide ("Insoluble" Cu compound, sub-micron size particles) as positive control and silica "seed" particles (without Cu loading) as negative control. Bacterial growth in solution was measured against different concentrations of C-S CuSiO2NP to determine the Minimum Inhibitory Concentration (MIC) value. The estimated MIC values were 2.4 microg metallic Cu/mL for both E. coli and B. subtilis. Bac-light fluorescence microscopy based assay was used to count relative population of the live and dead bacteria cells. Antibacterial study clearly shows that C-S CuSiO2NP is more effective than insoluble Cu hydroxide particles at equivalent metallic Cu concentration, suggesting improvement of Cu bioavailability (i.e., more soluble Cu) in C-SCuSiO2NP material due to its core-shell design. PMID

  12. Characterization of copper(II) complexes of N4, N4-disubstituted thiosemicarbazones of 2-acetylpyridine by combined evaluation of electronic and ESR parameters

    NASA Astrophysics Data System (ADS)

    Jain, Satendra K.; Garg, Bhagwan S.; Bhoon, Yudhvir K.

    Copper(II) complexes of 2-acetylpyridine 4,4-dimethyl-3-thiosemicarbazone (L'H) and 2-acetylpyridine 4-(4-methylpiperidinyl)-3-thiosemicarbazone (LH) of the general formula CuLX (where L is a deprotonated ligand and X = F -, Cl -, Br -, I -, OAc - and NO -3) have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements between 93 and 298 K in the polycrystalline state, i.r. spectra, electronic spectra, conductivity measurements and ESR spectra recorded in the polycrystalline state, in chloroform and dimethylformamide solution at room temperature and at 77K. The molar conductivities measured in dimethylformamide for all complexes show them to be non-electrolytes. The terdentate character of the ligands in all the complexes is inferred from i.r. spectral studies. The i.r. spectra also confirm the monodentate nature of the polyatomic anions such as nitrate and acetate. The electronic spectra in Nujol mulls, chloroform or dimethylformamide solution suggest planar geometry for all of the complexes. The calculated ESR parameters show an axial dx2- y2 ground state and suggest coordination through sulphur in agreement with the i.r. results. Little change in the value of g with temperature indicates no significant change in planarity of these four coordinated species. ESR spectra in solution at room temperature and 77 K also suggest a strong covalent environment with strong in-plane sigma and pi bonds provided by the ligands.

  13. Estrogen Receptor Alpha (ESR1)-Dependent Regulation of the Mouse Oviductal Transcriptome

    PubMed Central

    Cerny, Katheryn L.; Ribeiro, Rosanne A. C.; Jeoung, Myoungkun; Ko, CheMyong; Bridges, Phillip J.

    2016-01-01

    Estrogen receptor-α (ESR1) is an important transcriptional regulator in the mammalian oviduct, however ESR1-dependent regulation of the transcriptome of this organ is not well defined, especially at the genomic level. The objective of this study was therefore to investigate estradiol- and ESR1-dependent regulation of the transcriptome of the oviduct using transgenic mice, both with (ESR1KO) and without (wild-type, WT) a global deletion of ESR1. Oviducts were collected from ESR1KO and WT littermates at 23 days of age, or ESR1KO and WT mice were treated with 5 IU PMSG to stimulate follicular development and the production of ovarian estradiol, and the oviducts collected 48 h later. RNA extracted from whole oviducts was hybridized to Affymetrix Genechip Mouse Genome 430–2.0 arrays (n = 3 arrays per genotype and treatment) or reverse transcribed to cDNA for analysis of the expression of selected mRNAs by real-time PCR. Following microarray analysis, a statistical two-way ANOVA and pairwise comparison (LSD test) revealed 2428 differentially expressed transcripts (DEG’s, P < 0.01). Genotype affected the expression of 2215 genes, treatment (PMSG) affected the expression of 465 genes, and genotype x treatment affected the expression of 438 genes. With the goal of determining estradiol/ESR1-regulated function, gene ontology (GO) and bioinformatic pathway analyses were performed on DEG’s in the oviducts of PMSG-treated ESR1KO versus PMSG-treated WT mice. Significantly enriched GO molecular function categories included binding and catalytic activity. Significantly enriched GO cellular component categories indicated the extracellular region. Significantly enriched GO biological process categories involved a single organism, modulation of a measurable attribute and developmental processes. Bioinformatic analysis revealed ESR1-regulation of the immune response within the oviduct as the primary canonical pathway. In summary, a transcriptomal profile of estradiol- and ESR1

  14. Estrogen Receptor Alpha (ESR1)-Dependent Regulation of the Mouse Oviductal Transcriptome.

    PubMed

    Cerny, Katheryn L; Ribeiro, Rosanne A C; Jeoung, Myoungkun; Ko, CheMyong; Bridges, Phillip J

    2016-01-01

    Estrogen receptor-α (ESR1) is an important transcriptional regulator in the mammalian oviduct, however ESR1-dependent regulation of the transcriptome of this organ is not well defined, especially at the genomic level. The objective of this study was therefore to investigate estradiol- and ESR1-dependent regulation of the transcriptome of the oviduct using transgenic mice, both with (ESR1KO) and without (wild-type, WT) a global deletion of ESR1. Oviducts were collected from ESR1KO and WT littermates at 23 days of age, or ESR1KO and WT mice were treated with 5 IU PMSG to stimulate follicular development and the production of ovarian estradiol, and the oviducts collected 48 h later. RNA extracted from whole oviducts was hybridized to Affymetrix Genechip Mouse Genome 430-2.0 arrays (n = 3 arrays per genotype and treatment) or reverse transcribed to cDNA for analysis of the expression of selected mRNAs by real-time PCR. Following microarray analysis, a statistical two-way ANOVA and pairwise comparison (LSD test) revealed 2428 differentially expressed transcripts (DEG's, P < 0.01). Genotype affected the expression of 2215 genes, treatment (PMSG) affected the expression of 465 genes, and genotype x treatment affected the expression of 438 genes. With the goal of determining estradiol/ESR1-regulated function, gene ontology (GO) and bioinformatic pathway analyses were performed on DEG's in the oviducts of PMSG-treated ESR1KO versus PMSG-treated WT mice. Significantly enriched GO molecular function categories included binding and catalytic activity. Significantly enriched GO cellular component categories indicated the extracellular region. Significantly enriched GO biological process categories involved a single organism, modulation of a measurable attribute and developmental processes. Bioinformatic analysis revealed ESR1-regulation of the immune response within the oviduct as the primary canonical pathway. In summary, a transcriptomal profile of estradiol- and ESR1

  15. The ESR dosimetric features of strontium sulfate and temperature effects on radiation-induced signals

    NASA Astrophysics Data System (ADS)

    Acar, Ali Osman; Polat, Mustafa; Aydin, Talat; Aydaş, Canan

    2016-06-01

    In the present work, the ESR dosimetric potential of strontium sulfate has been investigated in the radiation dose range of 1-100 Gy. It does not exhibit any ESR signal before irradiation. However, irradiation produced three intensive resonance signals (A, B and C) which increase linearly in the studied dose range. Variable temperature study showed that all ESR signals were found to decrease significantly at temperatures higher than 340 K. Kinetic studies performed at high temperatures showed that at least two distinct radical species with the activation energy values of 42.8±3.6 and 88.2±5.8 kJ/mol, respectively, contributed to the ESR signal B.

  16. 19F NMR-, ESR-, and vis-NIR-spectroelectrochemical study of the unconventional reduction behaviour of a perfluoroalkylated fullerene: dimerization of the C70(CF3)10– radical anion†

    PubMed Central

    Zalibera, Michal; Machata, Peter; Clikeman, Tyler T.; Rosenkranz, Marco; Strauss, Steven H.; Boltalina, Olga V.; Popov, Alexey A.

    2016-01-01

    The most abundant isomer of C70(CF3)10 (70-10-1) is a rare example of a perfluoroalkylated fullerene exhibiting electrochemically irreversible reduction. We show that electrochemical reversibility at the first reduction step is achieved at scan rates higher than 500 V s-1 Applying ESR-, vis-NIR-, and 19F NMR- spectroelectrochemistry, as well as mass spectrometry and DFT calculations, we show that the (70-10-1)- radical monoanion is in equilibrium with a singly-bonded diamagnetic dimeric dianion. This study is the first example of 19F NMR spectroelectrochemistry, which promises to be an important method for the elucidation of redox mechanisms of fluoroorganic compounds. Additionally, we demonstrate the importance of combining different spectroelectrochemical methods and quantitative analysis of the transferred charge and spin numbers in the determination of the redox mechanism. PMID:26359514

  17. ESR study of. gamma. -irradiated substituted norbornanes in thiourea clathrate and adamantane matrix: novel 2-norbornyl-type radicals. [Irradiation at 77/sup 0/K

    SciTech Connect

    Faucitano, A.; Buttafava, A.; Martinotti, F.F.; Cesca, S.

    1981-02-19

    The ..gamma.. irradiation at 77/sup 0/K of 2-methyl-2-ethylbicyclo(2.2.1)heptane and of 2-methylene-2-ethylidenebicyclo(2.2.1)heptene in the state of thiourea adducts leads to formation of 2-methyl- and 2-ethylnorbornyl radicals by loss of hydrogen atoms at the substituent sites or by partial hydrogenation of the double bonds. On warming above 77/sup 0/K after irradiation, the 2-alkylnorbornyls add to double bonds of neighboring molecules yielding new adduct radicals alkylnorbornyl. The reactions can be reversed by uv irraidation at 77/sup 0/K, thus suggesting that the addition does not proceed beyond the first step. A reaction model based on the geometrical control by the molecular packing within the clathrate channels has been proposed. The irradiation of 2-ethylidenenorbornene in the state of thiourea clathrate or trapped in adamantane matrix yields an allyl-type radical by loss of a hydrogen atom from the methyl group. The structure and ESR properties of 2-alkylnorbornyls and of the allylnorbornyl have been investigated by MO methods to the INDO and extended Hueckel levels of approximation.

  18. Point defect study of CuTi and CuTi sub 2

    SciTech Connect

    Shoemaker, J.R.; Lutton, R.T.; Wesley, D.; Wharton, W.R.; Oehrli, M.L.; Herte, M.S.; Sabochick, M.J. ); Lam, N.Q. )

    1991-03-01

    The energies and configurations of interstitials and vacancies in the ordered compounds CuTi and CuTi{sub 2} were determined using atomistic simulation with realistic embedded-atom potentials. The formation energy of an antisite pair was found to be 0.385 and 0.460 eV in CuTi and CuTi{sub 2}, respectively. In both compounds, the creation of a vacancy by the removal of either a Cu or Ti atom resulted in a vacant Cu site, with an adjacent antisite defect in the case of the Ti vacancy. The vacant Cu site in CuTi was found to be very mobile within two adjacent (001) Cu planes, with a migration energy of 0.19 eV, giving rise to two-dimensional migration. The vacancy migration energy across (001) Ti planes, however, was 1.32 eV, which could be lowered to 0.75 or 0.60 eV if one or two Cu antisite defects were initially present in these planes. In CuTi{sub 2}, the vacancy migration energy of 0.92 eV along the (001) Cu plane was significantly higher than in CuTi. The effective vacancy formation energies were calculated to be 1.09 eV and 0.90 eV in CuTi and CuTi{sub 2}, respectively. Interstitials created by inserting either a Cu or Ti atom had complicated configurations in which a Cu {l angle}111{r angle} split interstitial was surrounded by two or three Ti antisite defects. The interstitial formation energy was estimated to be 1.7 eV in CuTi and 1.9 eV in CuTi{sub 2}.

  19. Identification of irradiated sage tea ( Salvia officinalis L.) by ESR spectroscopy

    NASA Astrophysics Data System (ADS)

    Tepe Çam, Semra; Engin, Birol

    2010-04-01

    The use of electron spin resonance (ESR) spectroscopy to accurately distinguish irradiated from unirradiated sage tea was examined. Before irradiation, sage tea samples exhibit one asymmetric singlet ESR signal centered at g=2.0037. Besides this central signal, two weak satellite signals situated about 3 mT left and right to it in radiation-induced spectra. Irradiation with increasing doses caused a significant increase in radiation-induced ESR signal intensity at g=2.0265 (the left satellite signal) and this increase was found to be explained by a polynomial varying function. The stability of that radiation-induced ESR signal at room temperature was studied over a storage period of 9 months. Also, the kinetic of signal at g=2.0265 was studied in detail over a temperature range 313-353 K by annealing samples at different temperatures for various times.

  20. Structural and optical studies of CuO nanostructures

    SciTech Connect

    Chand, Prakash Gaur, Anurag Kumar, Ashavani

    2014-04-24

    In the present study, copper oxide (CuO) nanostructures have been synthesized at 140 °C for different aging periods, 1, 24, 48 and 96 hrs by hydrothermal method to investigate their effects on structural and optical properties. The X-ray diffractometer (XRD) pattern indicates the pure phase formation of CuO and the particle size, calculated from XRD data, has been found to be increasing from 21 to 36 nm for the samples synthesized at different aging periods. Field emission scanning electron microscope (FESEM) analysis also shows that the average diameter and length of these rectangular nano flakes increases with increasing the aging periods. Moreover Raman spectrums also confirm the phase formation of CuO. The optical band gaps calculated through UV-visible spectroscopy are found to be decreasing from 2.92 to 2.69 eV with increase in aging periods, 1 to 96 hrs, respectively.

  1. Study of a splat cooled Cu-Zr-noncrystalline phase.

    NASA Technical Reports Server (NTRS)

    Revcolevschi, A.; Grant, N. J.

    1972-01-01

    By rapid quenching from the melt, using the splat forming gun technique, a noncrystalline phase has been obtained in a Cu-Zr alloy containing 60 at. % Cu. Upon heating, rapid crystallization of the samples takes place at 477 C with a heat release of about 700 cal per mol. The variation of the electrical resistivity of the samples with temperature confirms the transformation. Very high resolution electron microscopy studies of the structural changes of the samples upon heating are presented and show the gradual crystallization of the amorphous structure.

  2. ESR dating of mollusc shell: Investigations with modern shell of four species

    NASA Astrophysics Data System (ADS)

    Brumby, Steven; Yoshida, Hiroyuki

    The dose response curves for shells of four species of marine mollusc have been studied, using chiefly the g = 2.0014 (2 mW microwave power) and g = 2.0006 (60 mW power) ESR signals. The curves show variable inflexion points and conform only approximately to saturating exponentials with linear components. Annealing experiments suggest the possibility of using the ESR signal at g = 2.0058, after suitable heat treatment, for the estimation of accumulated doses.

  3. Synthesis, characterization and in vitro antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes derived from macrocyclic compartmental ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, O. A.; Bekheit, M. M.; El-Brashy, S. A.

    2015-02-01

    New Co(II), Ni(II) and Cu(II) complexes derived from tetradentate macrocyclic nitrogen ligand, (1E,4E,8E,12E)-5,8,13,16-tetramethyl-1,4,9,12-tetrazacyclohexadeca-4,8,12,16-tetraene (EDHDH) have been synthesized. The complexes have been characterized by elemental analysis, spectral (IR, UV-Vis, 1H NMR and ESR (for Cu(II) complex)) mass, and magnetic as well as thermal analysis measurements. The complexes afforded the formulae: [Cu(EDHDH)Cl2]·2EtOH and [M(EDHDH)X2]·nH2O where M = Co(II) and Ni(II), X = Cl- or OH-, n = 1,0, respectively. The data revealed an octahedral arrangement with N4 tetradentate donor sites in addition to two Cl atoms occupying the other two sites. ESR spectrum of Cu2+ complex confirmed the suggested geometry with values of a α2and β2 indicating that the in-plane σ-bonding and in-plane π-bonding are appreciably covalent, and are consistent with very strong σ-in-plane bonding in the complexes. The molecular modeling is drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds using DFT method. Also, the thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. Moreover, the in vitro antibacterial studies of all compounds screened against pathogenic bacteria (two Gram +ve and two Gram -ve) to assess their inhibiting potential. The assay indicated that the inhibition potential is metal ion dependent. The ligand, EDHDH, Co(II) and Cu(II) complexes exhibited a remarkable antibacterial activity against Streptococcus Pyogenes as Gram +ve and Proteus vulgaris as Gram -ve bacterial strains. On the other hand, Ni(II) complex revealed a moderate antibacterial activity against both Gram +ve organisms and no activity against Gram -ve bacterial strain.

  4. Synthesis, characterization and in vitro antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes derived from macrocyclic compartmental ligand.

    PubMed

    El-Gammal, O A; Bekheit, M M; El-Brashy, S A

    2015-02-25

    New Co(II), Ni(II) and Cu(II) complexes derived from tetradentate macrocyclic nitrogen ligand, (1E,4E,8E,12E)-5,8,13,16-tetramethyl-1,4,9,12-tetrazacyclohexadeca-4,8,12,16-tetraene (EDHDH) have been synthesized. The complexes have been characterized by elemental analysis, spectral (IR, UV-Vis, (1)H NMR and ESR (for Cu(II) complex)) mass, and magnetic as well as thermal analysis measurements. The complexes afforded the formulae: [Cu(EDHDH)Cl2]·2EtOH and [M(EDHDH)X2]·nH2O where M=Co(II) and Ni(II), X=Cl(-) or OH(-), n=1,0, respectively. The data revealed an octahedral arrangement with N4 tetradentate donor sites in addition to two Cl atoms occupying the other two sites. ESR spectrum of Cu(2+) complex confirmed the suggested geometry with values of a α(2)and β(2) indicating that the in-plane σ-bonding and in-plane π-bonding are appreciably covalent, and are consistent with very strong σ-in-plane bonding in the complexes. The molecular modeling is drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds using DFT method. Also, the thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. Moreover, the in vitro antibacterial studies of all compounds screened against pathogenic bacteria (two Gram +ve and two Gram -ve) to assess their inhibiting potential. The assay indicated that the inhibition potential is metal ion dependent. The ligand, EDHDH, Co(II) and Cu(II) complexes exhibited a remarkable antibacterial activity against Streptococcus Pyogenes as Gram +ve and Proteus vulgaris as Gram -ve bacterial strains. On the other hand, Ni(II) complex revealed a moderate antibacterial activity against both Gram +ve organisms and no activity against Gram -ve bacterial strain. PMID:25218230

  5. An attempt to model electrode change during the ESR process

    NASA Astrophysics Data System (ADS)

    Karimi-Sibaki, E.; Kharicha, A.; Wu, M.; Ludwig, A.; Holzgruber, H.; Ofner, B.; Scheriau, A.; Kubin, M.; Ramprecht, M.

    2016-07-01

    The electrode change technology is used to produce very large heavy ingots in which a number of electrodes are remelted one after another during the ESR process. Preparing the new electrode for remelting requires a certain period of time when the electric current is stopped (power off). Here, CFD simulation is used to study the behavior of a large scale ESR process during the electrode change (power off). Firstly, the electromagnetic, temperature, and turbulent flow fields in the process before electrode change are modelled. Mold current and thermal effect due to shrinkage of ingot is considered in the model. Then, a transient simulation is performed and the response of the system to the power off is continuously tracked. It is observed that the pool profile of ingot is preserved before and after electrode change. Details of the flow and temperature distributions during electrode change are presented in the paper.

  6. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands

    NASA Astrophysics Data System (ADS)

    Sumathi, S.; Tharmaraj, P.; Sheela, C. D.; Anitha, C.

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M = Cu(II), Ni(II), Co(II); L = 3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, 1H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

  7. Cluster model studies of oxygen-bridged Cu pairs in Cu-ZSM-5 catalysts

    SciTech Connect

    Goodman, B.R.; Hass, K.C.; Schneider, W.F.; Adams, J.B.

    1999-11-25

    Effects of the support environment on the existence of Cu ion pairs in Cu-exchanged ZSM-5 catalysts are examined using density functional theory. Results for the molecular and electronic structures of O- and O{sub 2}-bridged Cu oxocations ([CuOCu]{sup 2+} and [CuO{sub 2}Cu]{sup 2+}) are presented, including two distinct isomers for the latter. Both types of oxocations are predicted to be strongly bound for conditions likely to occur in the zeolite. The zeolite framework is represented by a variety of cluster models, including a previously established single-T-site model and larger multi-T-site models specific to particular binding sites in ZSM-5. With the largest models, bent Cu-O{sub x}-Cu structures are found with Cu-Cu distances consistent with X-ray absorption data for Cu-ZSM-5. Implications for catalytic chemistry, including a proposed pathway for O{sub 2} formation and subsequent desorption from oxidized Cu sites in the zeolite, are discussed.

  8. First-principles study of Al-Cu energetics and consequences on athermal formation of Cu-rich compounds

    NASA Astrophysics Data System (ADS)

    Besson, R.; Kwon, J.; Thuinet, L.; Avettand-Fènoël, M.-N.; Legris, A.

    2014-12-01

    In spite of its practical interest, the Al-Cu system remains largely unexplored, especially on its Cu-rich side. In order to improve the knowledge of this system, we perform a thorough ab initio study of fcc-based Al-Cu energetics, using the recently proposed M2BCE reciprocal-space cluster expansion approach. We demonstrate the existence of two clearly distinct composition domains, revealing complex ground-state properties. Below 50% Cu, the GP 2 -A l3Cu compound appears as highly favored, in agreement with the well-documented transformation sequence in Al-based alloys. Conversely, the domain between 50% and 80% Cu displays a much shallower landscape, characterized by the existence of a wealth of compounds undergoing fcc →bcc structural instabilities. While such "Bain paths" have been identified for a long time in iron-based alloys, our work gives evidence for their existence in the Al-Cu system. As a striking application, these instabilities provide plausible athermal mechanisms for the formation of Cu-rich phases, in particular for the unexpected emergence of γ1-A l4C u9 , a Hume-Rothery compound observed in various nonequilibrium conditions.

  9. Study of CuO Nano-particles/CuTl-1223 Superconductor Composite

    NASA Astrophysics Data System (ADS)

    Mumtaz, M.; Bhatti, Asif I.; Nadeem, K.; Khan, Nawazish A.; Saleem, Abida; Hussain, S. Tajammul

    2013-02-01

    Synthesis and characterization of (CuO) x /Cu0.5Tl0.5Ba2Ca2Cu3O10- δ ; {(CuO) x /CuTl-1223} composites with x=0 %, 10 %, 15 % and 20 % have been reported. The fluctuations induced conductivity (FIC) analysis of (CuO) x /CuTl-1223 composite has been carried out using Aslamazov-Larkin (AL) and Lawrence-Doniach (LD) models in the temperature regime well above the critical temperature ( T> T c ). The electrical resistivity versus temperature curves of as-prepared and oxygen post-annealed (CuO) x /CuTl-1223 composite were fitted by using above mentioned models to extract the microscopic parameters such as zero temperature coherence length along c-axis{ ξ c (0)}, inter-layer coupling ( J), dimensional critical exponent ( λ) and inter-grain coupling constant ( α) etc. It has been observed that the cross-over temperature ( T o ) fits very well the two-dimensional (2D) and three-dimensional (3D) AL equations and shifts towards the lower temperature regime with the enhanced weight percentage of CuO nano-particles. The shifting of AL 3D region to higher temperature after oxygen post-annealing indicates the restoration of oxygen and optimization of charge carriers in conducting CuO2 planes. The gradual decrease in the value of inter-grain coupling constant ( α) with the increase of CuO nano-particles content reflects an improvement in the inter-grain coupling resulting into an increase in the coherence length ( ξ c ) along the c-axis. Almost all superconductivity parameters have been improved after oxygen post-annealing. The suppression of superconductivity parameters in the composite with x=20 % limits the optimum doping level of CuO nano-particles in (CuO) x /CuTl-1223 composite.

  10. Transient melting of an ESR electrode

    NASA Astrophysics Data System (ADS)

    Kharicha, A.; Karimi-Sibaki, E.; Bohacek, J.; Wu, M.; Ludwig, A.

    2016-07-01

    Melting parameters of ESR process such as melt rate and immersion depth of electrode are of great importance. In this paper, a dynamic mesh based simulation framework is proposed to model melt rate and shape of electrode during the ESR process. Coupling interactions between turbulent flow, temperature, and electromagnetic fields are fully considered. The model is computationally efficient, and enables us to directly calculate melting parameters. Furthermore, dynamic change of electrode shape by melting can be captured. It is necessary to control the feeding velocity of electrode due to melting instabilities in the ESR process. As such, a numerical control is implemented based on the immersion depth of electrode to achieve the steady state in the simulation. Furthermore, the modeling result is evaluated against an experiment.

  11. ESR melting under constant voltage conditions

    SciTech Connect

    Schlienger, M.E.

    1997-02-01

    Typical industrial ESR melting practice includes operation at a constant current. This constant current operation is achieved through the use of a power supply whose output provides this constant current characteristic. Analysis of this melting mode indicates that the ESR process under conditions of constant current is inherently unstable. Analysis also indicates that ESR melting under the condition of a constant applied voltage yields a process which is inherently stable. This paper reviews the process stability arguments for both constant current and constant voltage operation. Explanations are given as to why there is a difference between the two modes of operation. Finally, constant voltage process considerations such as melt rate control, response to electrode anomalies and impact on solidification will be discussed.

  12. Influence of sample treatment on ESR signal of irradiated citrus.

    PubMed

    de Jesus, E F; Rossi, A M; Lopes, R T

    1996-01-01

    ESR spectra of the hard seed cover and kernel coating of irradiated orange and tangerine fruits were obtained under different sample drying conditions to analyze the effect of treatment on ESR line at g = 2.0033 (line A). The spectra shows almost the same lines that appear in stalks, achenes, seeds and skins of fresh fruit. The peak-to-peak intensity of the line A of the spectra shows a linear variation with dose in the range studied (up to 5 kGy) under controlled sample preparation. Q-band ESR spectra shows that this line is composed for three different lines from different species. A1, A2 and A3. The A2 and A3 lines are associated with dose but grow also during drying of the sample and are probably due to 'cellulosic' components of the seed cover. The A1 line appears only when sample is dried and is probably associated with the quinones of the internal kernel coat. PMID:9022204

  13. Synthesis, spectral, antitumor and antimicrobial studies on Cu(II) complexes of purine and triazole Schiff base derivatives

    NASA Astrophysics Data System (ADS)

    Amer, Said; El-Wakiel, Nadia; El-Ghamry, Hoda

    2013-10-01

    A series of copper (II) complexes of Schiff bases derived from 7H-2,6-diaminopurine and 4H-3,5-diamino-1,2,4-triazole with 2-pyridinecarbaldehyde, salicylaldehyde, 2,4-dihydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde have been prepared. The donor atoms and the possible geometry of the complexes were investigated by means of elemental and thermal analyses, molar conductance, magnetic moment, UV-Vis, IR, ESR and mass spectra. The ligands behaved as tetradentate, coordinating through the nitrogen atom of the azomethine group and the nearest nitrogen atom to it or oxygen atom of α-hydroxyl group. The results of simultaneous DTA & TGA analyses of the complexes showed the final degradation product for these complexes is CuO. The spectral studies confirmed a four coordinate environment around the metal ion. The obtained results were supported by 3D molecular modeling of complexes using molecular mechanics (MM+) and semiempirical molecular orbital calculations (PM3). These complexes were also tested for their in vitro antimicrobial activities against some bacterial and fungal strains. Complex 2 was investigated for its cyctotoxic effect against human breast cancer (MCF7), liver carcinoma (HEPG2) and colon carcinoma cell lines (HCT116). This compound exhibited a moderate activity against the tested cell lines with IC50 of 10.3, 9.8 and 8.7 μg/ml against MCF7, HCT116 and HEPG2, respectively.

  14. Properties of the Oxidized Cu(110) Surface: The DFT study

    NASA Astrophysics Data System (ADS)

    Olenga, Antoine; Fazleev, N. G.

    2012-10-01

    The study of adsorption of oxygen on transition metal surfaces is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. In this work we have studied from first principles the changes of electronic properties of the Cu(110) surface due to oxygen adsorption. Especially, we have focused on studies of changes in the work function, electronic density, interlayer spacing, density of states and band structure with oxygen coverage. Calculations of electronic properties from first principles have been also performed for the (110) and surface of Cu2O to use for comparison. The first-principles calculations in this work have been performed on the basis of the Density Functional Theory and using DMOl3 code. The obtained theoretical results have been compared with available experimental data.

  15. Association with litter size of new polymorphisms on ESR1 and ESR2 genes in a Chinese-European pig line

    PubMed Central

    Muñoz, Gloria; Ovilo, Cristina; Estellé, Jordi; Silió, Luis; Fernández, Almudena; Rodriguez, Carmen

    2007-01-01

    The objective of this study was to search for polymorphisms in the coding region of the estrogen receptors 1 and 2 (ESR1 and ESR2 )and to analyze the effects of these variants and the well known intronic ESR1 Pvu II polymorphism on litter size in a Chinese-European pig line. We identified five silent single nucleotide polymorphisms (SNP) in the ESR1 cDNA: c.669T > C (exon 3), c.1227C > T (exon 5), c.1452C > T (exon 7), c.1665T > C and c.1755A > G (exon 8). One pair of these SNP (c.1665T > C and c.1755A > G) co-segregated in the analyzed line, and the SNP c.669T > C showed the same segregation pattern as the Pvu II polymorphism. These polymorphisms were tested in this study, although the c.1452C > T SNP within exon 7 was not analyzed due to its low informativeness. In the ESR2 cDNA, one missense SNP was found within exon 5, which caused an amino acid substitution in the coded protein: "c.949G > A (p.Val317Met)" and was tested on sow litter size. Information on 1622 litter records from 408 genotyped sows was analyzed to determine whether these SNP influenced the total number of piglets born (TNB) or the number of born alive (NBA). The polymorphisms ESR1: [Pvu II; c.669T > C], ESR1: [c.1665T > C; c.1755A > G] and ESR2: c.949G > A showed no statistically significant association with litter size. However, the ESR1: c.1227T allele was significantly associated with TNB. The additive substitution effect was estimated to be 0.40 piglets born per litter (P < 0.03), and no dominance effects were observed. This SNP could be useful in assisted selection for litter size in some pig lines, as a new genetic marker in linkage disequilibrium with the causative mutation. PMID:17306201

  16. A XANES study of Cu speciation in high-temperature brines using synthetic fluid inclusions

    SciTech Connect

    Berry, Andrew J.; Hack, Alistair C.; Mavrogenes, John A.; Newville, Matthew; Sutton, Stephen R.

    2010-12-03

    Cu K-edge X-ray absorption near edge structure (XANES) spectra were recorded from individual synthetic brine fluid inclusions as a function of temperature up to 500 C. The inclusions serve as sample cells for high-temperature spectroscopic studies of aqueous Cu-Cl speciation. Cu{sup +} and Cu{sup 2+} can both be identified from characteristic pre-edge features. Mixed oxidation states can be deconvoluted using linear combinations of Cu{sup +} and Cu{sup 2+} spectra. This work illustrates how complex Cu XANES spectra can be interpreted successfully. Cu{sup 2+} is the stable oxidation state in solution at room temperature and Cu{sup +} at high temperatures. The change in oxidation state with temperature was completely reversible. Cu{sup +} was found to occur exclusively as the linear species [CuCl{sub 2}]{sup -} in solutions containing KCl with Cu:Cl ratios up to 1:6. In the absence of K{sup +}, there is evidence for higher order coordination of Cu{sup +}, in particular the tetrahedral complex [CuCl{sub 4}]{sup 3-}. The importance of such complexes in natural ore-forming fluids is yet to be determined, but may explain the vapor-phase partitioning of Cu as a Cl complex from a Cl-rich brine.

  17. An invasive and low virulent Edwardsiella tarda esrB mutant promising as live attenuated vaccine in aquaculture.

    PubMed

    Yang, Weizheng; Wang, Lixia; Zhang, Lingzhi; Qu, Jiangbo; Wang, Qiyao; Zhang, Yuanxing

    2015-02-01

    Edwardsiella tarda is a leading fish pathogen haunting worldwide aquaculture industry. In E. tarda, two-component system EsrA-EsrB positively regulates type III and VI secretion systems (T3SS and T6SS) and negatively regulates hemolysin EthA, which has been demonstrated to be essential for the invasion processes in fish. In order to develop a live attenuated vaccine (LAV) with high invasiveness to be practically and economically used as immersion-administered vaccine in aquaculture, here, we generated a random mutation library of esrB sequences by error-prone PCR and introduced them into the E. tarda esrB deletion mutant. The mutant YWZ47 with significantly increased hemolytic activity and low T3SS and T6SS secretion was screened. Phenotypes including extracellular protein profiles, invasion in macrophages, lethality toward fish, and infection kinetics were investigated in the wild-type strain EIB202 and the mutants ΔesrB, ΔT3SS, ΔT6SS, ΔT3SS/ΔT6SS, and YWZ47. Compared to the documented LAV strain ΔesrB, YWZ47 showed higher invasive capability and low in vivo virulence toward fish. Significantly higher relative percent survival (RPS) could be generated in turbot (Scophthalmus maximus) against the challenge of the wild-type EIB202 when inoculated through immersion route, and the RPS was comparable with that of ΔesrB through intraperitoneal (i.p.) injection inoculation. Two mutated points, K167M and H197L, were found by sequence analysis of EsrBYWZ47 variant. These structural modifications underpin the variations in the regulatory functions of the mutant and wild-type EsrB. This study promoted understanding of virulence regulation by EsrB in E. tarda and presented a promising candidate of invasive attenuated vaccine used in aquaculture industries. PMID:25431010

  18. Fundamental Studies of Methanol Synthesis from CO2 Hydrogenation on Cu(111), Cu Clusters, and Cu/ZnO(000ī)

    SciTech Connect

    Liu, P.; Yang, Y.; Evans, J.; Rodriguez, J.A.; White, M.G.

    2010-06-21

    A combination of experimental and theoretical methods were employed to investigate the synthesis of methanolvia CO{sub 2}hydrogenation (CO{sub 2} + 3H{sub 2} {yields} CH{sub 3}OH + H{sub 2}O) on Cu(111) and Cunanoparticle surfaces. High pressure reactivity studies show that Cunanoparticles supported on a ZnO(000{bar 1}) single crystal exhibit a higher catalytic activity than the Cu(111) planar surface. Complementary density functional theory (DFT) calculations of methanol synthesis were also performed for a Cu(111) surface and unsupported Cu{sub 29} nanoparticles, and the results support a higher activity for Cu nanoparticles. The DFT calculations show that methanol synthesis on Cu surfaces proceeds through a formate intermediate and the overall reaction rate is limited by both formate and dioxomethylene hydrogenation. Moreover, the superior activity of the nanoparticle is associated with its fluxionality and the presence of low-coordinated Cu sites, which stabilize the key intermediates, e.g. formate and dioxomethylene, and lower the barrier for the rate-limiting hydrogenation process. The reverse water-gas-shift (RWGS) reaction (CO{sub 2} + H{sub 2} {yields} CO + H{sub 2}O) was experimentally observed to compete with methanol synthesis and was also considered in our DFT calculations. In agreement with experiment, the rate of the RWGS reaction on Cu nanoparticles is estimated to be 2 orders of magnitude faster than methanol synthesis at T = 573 K. The experiments and calculations also indicate that CO produced by the fast RWGS reaction does not undergo subsequent hydrogenation to methanol, but instead simply accumulates as a product. Methanol production from CO hydrogenation via the RWGS pathway is hindered by the first hydrogenation of CO to formyl, which is not stable and prefers to dissociate into CO and H atoms on Cu. Our calculated results suggest that the methanol yield over Cu-based catalysts could be improved by adding dopants or promoters which are able

  19. Component, Microstructure and Simulation Calculation Study of Bimetallic Pt-Cu Alloys Towards Catalyzing Methanol Oxidation Reaction

    NASA Astrophysics Data System (ADS)

    Wei, Shenying; Gao, Huaizhi; Li, Haibo; Li, Rui; Liu, Jifeng

    2014-12-01

    Three Pt-Cu alloys (Pt0.3Cu0.7, Pt0.5Cu0.5, and Pt0.7Cu0.3) with different Cu contents were synthesized by adjusting the Pt/Cu precursor ratio, and their electrocatalytic activities for methanol oxidation reaction (MOR) were systematically studied. Component and microstructure study revealed that the relationship between the lattice parameters and Cu content followed the Vegard's law. Electrochemistry measurement showed that the MOR catalytic activity for Pt-Cu alloys displayed a dependency on the Cu content, and it decreased following: Pt0.3Cu0.7 > Pt0.5Cu0.5 > Pt0.7Cu0.3. Among the three Pt-Cu alloys, the Pt0.3Cu0.7 alloy exhibited the highest oxidation current density and best CO tolerance activity. Density functional theory simulation calculation, taking into account the shrinking of Pt-Cu alloy's lattice after Cu incorporation, confirmed that the adsorption energy of CO also displayed a dependency on the Cu content in Pt-Cu alloys, and it increased following: Pt0.3Cu0.7 < Pt0.5Cu0.5 < Pt0.7Cu0.3 < Pt, which could rationally explain the best CO tolerance ability for the Pt0.3Cu0.7.

  20. Educating for Social Responsibility. The ESR Journal.

    ERIC Educational Resources Information Center

    Pittman, Susan Peters, Ed.

    1990-01-01

    Dedicated to Seth Kreisberg, this document is the first journal issue of the Educators for Social Responsibility (ESR). It begins with "The Real Ropes Course: The Development of Social Consciousness" (Shelley Berman). The other articles are presented in five sections. The first section, "Our Relationship to Society," contains: (1) "What Should…

  1. An ESR Investigation of Synthetic Pyrite Crystals

    NASA Astrophysics Data System (ADS)

    Siebert, D.; Dahlem, J.; Fiechter, S.; Hartmann, A.

    1989-01-01

    Synthetic pyrite crystals doped with halogen (CI, Br) or manganese (Mn) were investigated by ESR at 78 K with an X-band spectrometer and a TE102 cavity with 100 kc field modulation. The crystals were preferably measured with the directions <100>, <110>, and <111> parallel to the static magnetic field HO. The ESR spectrum of Mn-doped crystals showed a sextet which can be explained by a spin-Hamiltonian for an electron spin S = 1/2 in interaction with the nuclear spin I = 5/2 of the Mn nucleus for axial symmetry. Due to the observed spin and due to the orientation of the paramagnetic centers the spectra were assigned to Mn2+ in the low spin state which resides on cation site in the FeS2, lattice. In halogen-doped crystals four pairs of lines can be interpreted by the interaction of the two isotopes of I = 3/2, 79Br, 81Br and 35Cl, 37Cl, respectively, with an electron spin S = 1/2. According to the observed symmetry of the ESR signals the paramagnetic centers can be explained as (S-X)2- radicals (X = CI, Br) which substitute for the (S2)2- dumb-bells of pyrite. All crystals evoked extremely narrow ESR lines, especially the halogen-doped crystals with linewidths down to 0.03 mT. Excellent agreement between measured and calculated spectra up to the finest details has been obtained.

  2. ESR Measurement Of Crystallinity In Semicrystalline Polymers

    NASA Technical Reports Server (NTRS)

    Kim, Soon Sam; Tsay, Fun-Dow

    1989-01-01

    Photogenerated free radicals decay at different rates in crystalline and amorphous phases. Degree of crystallinity in polymer having both crystalline and amorphous phases measured indirectly by technique based in part on electron-spin-resonance (ESR) spectroscopy. Accuracy of crystallinity determined by new technique equals or exceeds similar determinations by differential scanning calorimetry, wide-angle x-ray scattering, or measurement of density.

  3. DNA cleavage, antibacterial, antifungal and anthelmintic studies of Co(II), Ni(II) and Cu(II) complexes of coumarin Schiff bases: Synthesis and spectral approach

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Prabhakara, Chetan T.; Halasangi, Bhimashankar M.; Toragalmath, Shivakumar S.; Badami, Prema S.

    2015-02-01

    The metal complexes of Co(II), Ni(II) and Cu(II) have been synthesized from 6-formyl-7,8-dihydroxy-4-methylcoumarin with o-toluidine/3-aminobenzotrifluoride. The synthesized Schiff bases and their metal complexes were structurally characterized based on IR, 1H NMR, 13C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The molar conductance values indicate that complexes are non-electrolytic in nature. Elemental analysis reveals ML2·2H2O [M = Co(II), Ni(II) and Cu(II)] stoichiometry, where 'L' stands for a singly deprotonated ligand. The presence of co-ordinated water molecules were confirmed by thermal studies. The spectroscopic studies suggest the octahedral geometry. Redox behavior of the complexes were confirmed by cyclic voltammetry. All the synthesized compounds were screened for their antibacterial (Escherichia coli, Pseudomonas auregenosa, klebsiella, Proteus, Staphylococcus aureus and salmonella) antifungal (Candida, Aspergillus niger and Rhizopus), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activity.

  4. Study of UV Cu + Ne – CuBr laser lifetime by statistical methods

    SciTech Connect

    Iliev, I P; Gocheva-Ilieva, S G

    2013-11-30

    On the basis of a large amount of experimental data, statistical investigation of the average lifetime of a UV Cu + Ne – CuBr laser depending on ten input physical laser parameters is carried out. It is found that only three of the parameters have a substantial influence on the laser lifetime. Physical analysis and interpretation of the results are provided. (lasers)

  5. Dynamics of 4-oxo-TEMPO-d16-(15)N nitroxide-propylene glycol system studied by ESR and ESE in liquid and glassy state in temperature range 10-295K.

    PubMed

    Goslar, Janina; Hoffmann, Stanislaw K; Lijewski, Stefan

    2016-08-01

    ESR spectra and electron spin relaxation of nitroxide radical in 4-oxo-TEMPO-d16-(15)N in propylene glycol were studied at X-band in the temperature range 10-295K. The spin-lattice relaxation in the liquid viscous state determined from the resonance line shape is governed by three mechanisms occurring during isotropic molecular reorientations. In the glassy state below 200K the spin-lattice relaxation, phase relaxation and electron spin echo envelope modulations (ESEEM) were studied by pulse spin echo technique using 2-pulse and 3-pulse induced signals. Electron spin-lattice relaxation is governed by a single non-phonon relaxation process produced by localized oscillators of energy 76cm(-1). Electron spin dephasing is dominated by a molecular motion producing a resonance-type peak in the temperature dependence of the dephasing rate around 120K. The origin of the peak is discussed and a simple method for the peak shape analysis is proposed, which gives the activation energy of a thermally activated motion Ea=7.8kJ/mol and correlation time τ0=10(-8)s. The spin echo amplitude is strongly modulated and FT spectrum contains a doublet of lines centered around the (2)D nuclei Zeeman frequency. The splitting into the doublet is discussed as due to a weak hyperfine coupling of nitroxide unpaired electron with deuterium of reorienting CD3 groups. PMID:27323281

  6. Dynamics of 4-oxo-TEMPO-d16-15N nitroxide-propylene glycol system studied by ESR and ESE in liquid and glassy state in temperature range 10-295 K

    NASA Astrophysics Data System (ADS)

    Goslar, Janina; Hoffmann, Stanislaw K.; Lijewski, Stefan

    2016-08-01

    ESR spectra and electron spin relaxation of nitroxide radical in 4-oxo-TEMPO-d16-15N in propylene glycol were studied at X-band in the temperature range 10-295 K. The spin-lattice relaxation in the liquid viscous state determined from the resonance line shape is governed by three mechanisms occurring during isotropic molecular reorientations. In the glassy state below 200 K the spin-lattice relaxation, phase relaxation and electron spin echo envelope modulations (ESEEM) were studied by pulse spin echo technique using 2-pulse and 3-pulse induced signals. Electron spin-lattice relaxation is governed by a single non-phonon relaxation process produced by localized oscillators of energy 76 cm-1. Electron spin dephasing is dominated by a molecular motion producing a resonance-type peak in the temperature dependence of the dephasing rate around 120 K. The origin of the peak is discussed and a simple method for the peak shape analysis is proposed, which gives the activation energy of a thermally activated motion Ea = 7.8 kJ/mol and correlation time τ0 = 10-8 s. The spin echo amplitude is strongly modulated and FT spectrum contains a doublet of lines centered around the 2D nuclei Zeeman frequency. The splitting into the doublet is discussed as due to a weak hyperfine coupling of nitroxide unpaired electron with deuterium of reorienting CD3 groups.

  7. Synthesis, structural characterization, thermal and electrochemical studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes containing thiazolylazo ligands

    NASA Astrophysics Data System (ADS)

    Chavan, S. S.; Sawant, V. A.

    2010-02-01

    Some thiazolylazo derivatives and their metal complexes of the type [M(L)(H 2O)Cl]; M = Mn(II), Co(II), Ni(II), Cu(II) and L = 6-(2'-thiazolylazo)-2-mercapto-quinazolin-4-one (HL 1), 6-(4'-phenyl-2'-thiazolylazo)-2-mercapto-quinazolin-4-one (HL 2), 6-(2'-thiazolylazo)-2-mercapto-3-( m-tolyl)-quinazolin-4-one (HL 3) and 6-(4'-phenyl-2'-thiazolylazo)-2-mercapto-3-( m-tolyl)-quinazolin-4-one (HL 4) have been prepared. All the complexes were characterized on the basis of elemental analysis, molar conductance, magnetic moment, IR, UV-vis, ESR, TG-DTA and powder X-ray diffraction studies. IR spectra of these complexes reveal that the complex formation occurred through thiazole nitrogen, azo nitrogen, imino nitrogen and sulfur atom of the ligands. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for the Mn(II), Co(II) and Ni(II) complexes and distorted octahedral geometry for the Cu(II) complexes. Electrochemical behavior of Ni(II) complexes exhibit quasireversible oxidation corresponding to Ni(III)/Ni(II) couple along with ligand reduction. X-ray diffraction study is used to elucidate the crystal structure of the complexes.

  8. Heterogeneity and clinical significance of ESR1 mutations in ER-positive metastatic breast cancer patients receiving fulvestrant

    PubMed Central

    Spoerke, Jill M.; Gendreau, Steven; Walter, Kimberly; Qiu, Jiaheng; Wilson, Timothy R.; Savage, Heidi; Aimi, Junko; Derynck, Mika K.; Chen, Meng; Chan, Iris T.; Amler, Lukas C.; Hampton, Garret M.; Johnston, Stephen; Krop, Ian; Schmid, Peter; Lackner, Mark R.

    2016-01-01

    Mutations in ESR1 have been associated with resistance to aromatase inhibitor (AI) therapy in patients with ER+ metastatic breast cancer. Little is known of the impact of these mutations in patients receiving selective oestrogen receptor degrader (SERD) therapy. In this study, hotspot mutations in ESR1 and PIK3CA from ctDNA were assayed in clinical trial samples from ER+ metastatic breast cancer patients randomized either to the SERD fulvestrant or fulvestrant plus a pan-PI3K inhibitor. ESR1 mutations are present in 37% of baseline samples and are enriched in patients with luminal A and PIK3CA-mutated tumours. ESR1 mutations are often polyclonal and longitudinal analysis shows distinct clones exhibiting divergent behaviour over time. ESR1 mutation allele frequency does not show a consistent pattern of increases during fulvestrant treatment, and progression-free survival is not different in patients with ESR1 mutations compared with wild-type patients. ESR1 mutations are not associated with clinical resistance to fulvestrant in this study. PMID:27174596

  9. Comprehensive genetic assessment of the ESR1 locus identifies a risk region for endometrial cancer.

    PubMed

    O'Mara, Tracy A; Glubb, Dylan M; Painter, Jodie N; Cheng, Timothy; Dennis, Joe; Attia, John; Holliday, Elizabeth G; McEvoy, Mark; Scott, Rodney J; Ashton, Katie; Proietto, Tony; Otton, Geoffrey; Shah, Mitul; Ahmed, Shahana; Healey, Catherine S; Gorman, Maggie; Martin, Lynn; Hodgson, Shirley; Fasching, Peter A; Hein, Alexander; Beckmann, Matthias W; Ekici, Arif B; Hall, Per; Czene, Kamila; Darabi, Hatef; Li, Jingmei; Dürst, Matthias; Runnebaum, Ingo; Hillemanns, Peter; Dörk, Thilo; Lambrechts, Diether; Depreeuw, Jeroen; Annibali, Daniela; Amant, Frederic; Zhao, Hui; Goode, Ellen L; Dowdy, Sean C; Fridley, Brooke L; Winham, Stacey J; Salvesen, Helga B; Njølstad, Tormund S; Trovik, Jone; Werner, Henrica M J; Tham, Emma; Liu, Tao; Mints, Miriam; Bolla, Manjeet K; Michailidou, Kyriaki; Tyrer, Jonathan P; Wang, Qin; Hopper, John L; Peto, Julian; Swerdlow, Anthony J; Burwinkel, Barbara; Brenner, Hermann; Meindl, Alfons; Brauch, Hiltrud; Lindblom, Annika; Chang-Claude, Jenny; Couch, Fergus J; Giles, Graham G; Kristensen, Vessela N; Cox, Angela; Pharoah, Paul D P; Dunning, Alison M; Tomlinson, Ian; Easton, Douglas F; Thompson, Deborah J; Spurdle, Amanda B

    2015-10-01

    Excessive exposure to estrogen is a well-established risk factor for endometrial cancer (EC), particularly for cancers of endometrioid histology. The physiological function of estrogen is primarily mediated by estrogen receptor alpha, encoded by ESR1. Consequently, several studies have investigated whether variation at the ESR1 locus is associated with risk of EC, with conflicting results. We performed comprehensive fine-mapping analyses of 3633 genotyped and imputed single nucleotide polymorphisms (SNPs) in 6607 EC cases and 37 925 controls. There was evidence of an EC risk signal located at a potential alternative promoter of the ESR1 gene (lead SNP rs79575945, P=1.86×10(-5)), which was stronger for cancers of endometrioid subtype (P=3.76×10(-6)). Bioinformatic analysis suggests that this risk signal is in a functionally important region targeting ESR1, and eQTL analysis found that rs79575945 was associated with expression of SYNE1, a neighbouring gene. In summary, we have identified a single EC risk signal located at ESR1, at study-wide significance. Given SNPs located at this locus have been associated with risk for breast cancer, also a hormonally driven cancer, this study adds weight to the rationale for performing informed candidate fine-scale genetic studies across cancer types. PMID:26330482

  10. Comprehensive genetic assessment of the ESR1 locus identifies a risk region for endometrial cancer

    PubMed Central

    O’Mara, Tracy A; Glubb, Dylan M; Painter, Jodie N; Cheng, Timothy; Dennis, Joe; Attia, John; Holliday, Elizabeth G; McEvoy, Mark; Scott, Rodney J; Ashton, Katie; Proietto, Tony; Otton, Geoffrey; Shah, Mitul; Ahmed, Shahana; Healey, Catherine S; Gorman, Maggie; Martin, Lynn; Hodgson, Shirley; Fasching, Peter A; Hein, Alexander; Beckmann, Matthias W; Ekici, Arif B; Hall, Per; Czene, Kamila; Darabi, Hatef; Li, Jingmei; Dürst, Matthias; Runnebaum, Ingo; Hillemanns, Peter; Dörk, Thilo; Lambrechts, Diether; Depreeuw, Jeroen; Annibali, Daniela; Amant, Frederic; Zhao, Hui; Goode, Ellen L; Dowdy, Sean C; Fridley, Brooke L; Winham, Stacey J; Salvesen, Helga B; Njølstad, Tormund S; Trovik, Jone; Werner, Henrica MJ; Tham, Emma; Liu, Tao; Mints, Miriam; Bolla, Manjeet K; Michailidou, Kyriaki; Tyrer, Jonathan P; Wang, Qin; Hopper, John L; Peto, Julian; Swerdlow, Anthony J; Burwinkel, Barbara; Brenner, Hermann; Meindl, Alfons; Brauch, Hiltrud; Lindblom, Annika; Chang-Claude, Jenny; Couch, Fergus J; Giles, Graham G; Kristensen, Vessela N; Cox, Angela; Pharoah, Paul D P; Dunning, Alison M; Tomlinson, Ian; Easton, Douglas F; Thompson, Deborah J; Spurdle, Amanda B

    2015-01-01

    Excessive exposure to estrogen is a well-established risk factor for endometrial cancer (EC), particularly for cancers of endometrioid histology. The physiological function of estrogen is primarily mediated by estrogen receptor alpha, encoded by ESR1. Consequently, several studies have investigated whether variation at the ESR1 locus is associated with risk of EC, with conflicting results. We performed comprehensive fine-mapping analyses of 3,633 genotyped and imputed single nucleotide polymorphisms (SNPs) in 6,607 EC cases and 37,925 controls. There was evidence of an EC risk signal located at a potential alternative promoter of the ESR1 gene (lead SNP rs79575945, P = 1.86 × 10−5), which was stronger for cancers of endometrioid subtype (P = 3.76 × 10−6). Bioinformatic analysis suggests that this risk signal is in a functionally important region targeting ESR1, and eQTL analysis found that rs79575945 was associated with expression of SYNE1, a neighbouring gene. In summary, we have identified a single EC risk signal located at ESR1, at study-wide significance. Given SNPs located at this locus have been associated with risk for breast cancer, also a hormonally driven cancer, this study adds weight to the rationale for performing informed candidate fine-scale genetic studies across cancer types. PMID:26330482

  11. Study of Electromigration-Induced Failures on Cu Pillar Bumps Joined to OSP and ENEPIG Substrates

    NASA Astrophysics Data System (ADS)

    Hsiao, Yu-Hsiang; Lin, Kwang-Lung; Lee, Chiu-Wen; Shao, Yu-Hsiu; Lai, Yi-Shao

    2012-12-01

    This work studies electromigration (EM)-induced failures on Cu pillar bumps joined to organic solderability preservative (OSP) on Cu substrates (OSP-bumps) and electroless Ni(P)/electroless Pd/immersion Au (ENEPIG) under bump metallurgy (UBM) on Cu substrates (ENEPIG-bumps). Two failure modes (Cu pad consumption and gap formation) were found with OSP-bumps, but only one failure mode (gap formation) was found with ENEPIG-bumps. The main interfacial compound layer was the Cu6Sn5 compound, which suffered significant EM-induced dissolution, eventually resulting in severe Cu pad consumption at the cathode side for OSP-bumps. A (Cu,Ni)6Sn5 layer with strong resistance to EM-induced dissolution exists at the joint interface when a nickel barrier layer is incorporated at the cathode side (Ni or ENEPIG), and these imbalanced atomic fluxes result in the voids and gap formation. OSP-bumps showed better lifetime results than ENEPIG-bumps for several current stressing conditions. The inverse Cu atomic flux ( J Cu,chem) which diffuses from the Cu pad to cathode side retards the formation of voids. The driving force for J Cu,chem comes from the difference in chemical potential between the (Cu,Ni)6Sn5 and Cu6Sn5 phases.

  12. A spectroscopic study of the reaction of Cu atoms with CO in a rotating cryostat: Evidence for the formation of CuCO, Cu(CO) sub 3 , and Cu sub 2 (CO) sub 6

    SciTech Connect

    Chenier, J.H.B.; Hampson, C.A.; Howard, J.A.; Mile, B. )

    1989-01-12

    Reaction of {sup 63}Cu atoms with CO has been studied in inert hydrocarbon matrices in a rotating cryostat at 77 K at EPR, FTIR, and UV/visible spectroscopy. CuCO and Cu(CO){sub 3} have been identified by EPR spectroscopy. CuCO has the magnetic parameters a{sub 63} = 3961 MHz, a{sub 13} = 191 MHz, and g = 1.9966 and is a linear molecule with most of the unpaired spin located in an sp-hybridized orbital on Cu. It is unstable and disappears rapidly above 77 K. Cu(CO){sub 3} is a planar trigonal {pi} radical with a {sup 2}A{sub 2}{prime}{prime} electronic ground state and a{sub 17} = 11.2 MHz which indicates significant unpaired spin population on the ligands. It has three infrared bands at 1998, 1988, and 1978 cm{sup {minus}1} which are assigned to the CO stretching mode of a D{sub 3h} molecule in three different trapping sites and is significantly more stable than CuCO. There are no bands in the FTIR spectra from Cu(CO){sub 2}. Cu{sub 2}(CO){sub 6} is formed in significant yields in adamantane and cyclohexane at 77 K and has a major CO stretching mode at 2035 cm{sup {minus}1}. Optical spectra of Cu(CO){sub 3} and Cu{sub 2}(CO){sub 6} in adamantane have {sup 2}A{sub 1}{prime} {l arrow} {sup 2}A{sub 2}{prime}{prime} and {sigma}* {l arrow} {sigma} electronic transitions at 565 and 405 nm, respectively.

  13. ESR study of the interaction of O/sub 2//sup -/ radical anions with aromatic molecules on V/SiO/sub 2/, V/ZrO/sub 2/, and V/MgO catalysts

    SciTech Connect

    Gasymov, A.M.; Shvets, V.A.; Kazanskii, V.B.

    1983-02-01

    The reactivity of O/sub 2//sup -/ radical anions adsorbed on supported V/SiO/sub 2/, V/ZrO/sub 2/, and V/MgO catalysts in reactions with benzene, toluene, and o-xylene molecules has been studied quantitatively with the aid of ESR by comparing the rate constants of the elementary steps. It has been found that the reactivity of O/sub 2//sup -/ interacting with benzene, toluene, and o-xylene molecules increases along the series C/sub 6/H/sub 6/ less than or equal to C/sub 6/H/sub 5/CH/sub 3/ less than or equal to C/sub 6/H/sub 4/ (CH/sub 3/)/sub 2/ and that the activity of the radical anions on the catalysts investigated increases along the series V/MgO less than or equal to V/ZrO/sub 2/ less than or equal to V/SiO/sub 2/. The main products of the reaction of O/sub 2//sup -/ radical anions adsorbed on V/SiO/sub 2/ and V/ZrO/sub 2/ catalysts with benzene and o-xylene molecules at 150-250/sup 0/C were the products of thorough oxidation.

  14. 1,3,5-Benzenetribenzoic Acid on Cu(111) and Graphene/Cu(111): A Comparative STM Study

    PubMed Central

    2016-01-01

    The self-assembly of 1,3,5-benzenetribenzoic acid (BTB) molecules on both Cu(111) and epitaxial graphene grown on Cu(111) were studied by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) under ultrahigh vacuum conditions. On Cu(111), the BTB molecules were found to mainly arrange in close-packed structures through H-bonding between the (partially) deprotonated carboxylic acid groups. In addition, porous structures formed by intact BTB molecules-and also based on H-bonding-were observed. On graphene grown on Cu(111) the BTB molecules mainly form porous structures accompanied by small patches of disordered close-packed structures. Upon annealing, BTB adsorbed on Cu(111) is fully deprotonated and arranges in the close-packed structure while in contrast on graphene/Cu(111) the porous network is exclusively formed. This shows that the molecular self-assembly behavior is highly dependent on the first substrate layer: one graphene layer is sufficient to considerably alter the interplay of molecule substrate and intermolecular interactions in favor of the latter interactions. PMID:27588158

  15. Manufacturing of 9CrMoCoB Steel of Large Ingot with Homogeneity by ESR Process

    NASA Astrophysics Data System (ADS)

    Kim, D. S.; Lee, G. J.; Lee, M. B.; Hur, J. I.; Lee, J. W.

    2016-07-01

    In case of 9CrMoCoB (COST FB2) steel, equilibrium relation between [B]/[Si] ratio and (B2O3)/(SiO2) ratio is very important to control [Si] and [B] in optimum range. Therefore, in this work, to investigate the thermodynamic equilibrium relation between [B]/[Si] ratio and (B2O3)/(SiO2) ratio, pilot ESR experiments of 9CrMoCoB steel were carried out using the CaF2-CaO-Al2O3-SiO2-B2O3 slag system according to change of Si content in electrode and B2O3 content in the slag. Furthermore, through the test melting of the 20ton-class ESR ingot, the merits and demerits of soft arcing were investigated. From these results, it is concluded that oxygen content in the ESR ingot decrease with decreasing SiO2 content in the slag, relation function between [B]/[Si] ratio and (B2O3)/(SiO2) ratio derived by Pilot ESR test shows a good agreement as compared to the calculated line with a same slope and soft arcing makes interior and surface quality of ingot worse. With the optimized ESR conditions obtained from the present study, a 1000mm diameter (20 tons) and 2200mm diameter (120ton) 9CrMoCoB steel of the ESR ingot were successfully manufactured with good homogeneity by the ESR process.

  16. Comparative NMR study of copper-based intermetallics with ZrCuSiAs-type structure

    NASA Astrophysics Data System (ADS)

    Lue, C. S.; ChangJen, W. J.; Su, T. H.

    2010-07-01

    The electronic characteristics of ZrCuGe2, ZrCuSi2, and HfCuSi2 are systematically investigated using C63u NMR spectroscopy. The quadrupole splittings, Knight shifts, and spin-lattice relaxation times on each individual compound have been identified. We found that the observed electric field gradient is consistent with the covalent bonding nature within the Cu atomic layers. The Knight shifts together with relaxation rates provide a measure of Cu d partial Fermi-level density of states, Nd(EF). Universally small Nd(EF) was found in all studied materials, suggests that the Cu d states are well below the Fermi energy and therefore the characteristic electronic structure near EF is primarily of sp type. We further pointed out that the low Nd(EF) value is an important factor for the lack of superconductivity in these Cu-based intermetallics within the ZrCuSiAs-type structure.

  17. Adsorption of Cu(II) on the (0001) plane of mica: A REFLEXAFS and XPS study

    SciTech Connect

    Farquhar, M.L.; England, K.E.R.; Vaughan, D.J.; Charnock, J.M. |

    1996-02-10

    Using reflection extended X-ray absorption fine structure spectroscopy (REFLEXAFS) and X-ray photoelectron spectroscopy (XPS) it has been established that Cu(II) in low concentration in aqueous media can be chemisorbed onto the (0001) surface of muscovite mica. From the XPS studies it is suggested that the Cu species is in a similar bonding environment to the copper in copper hydroxide. A depth profile of the reacted mica surface was also carried out using XPS and this suggests that there had been no diffusion of the Cu into the mica surface. REFLEXAFS studies of the reacted mica surface provided information about shells of O, AlSi, and Cu surrounding a central Cu absorber. The best-fit bond distances are as follows: O{single_bond}Cu, 1.98 {angstrom}; Cu{single_bond}Cu, 2.64 {angstrom}; Al/Si{single_bond}Cu, 3.09 {angstrom}. This provides direct evidence for Cu being bound to the surface at aluminate or silicate groups and suggests that the Cu species adsorbed onto the surface are similar to the copper species found in copper hydroxide, plancheite, and shattuckite. It is proposed that Cu is chemisorbed at atomic imperfections, such as steps and kinks, on the mica surface.

  18. Development of multi-frequency ESR system for high-pressure measurements up to 2.5 GPa

    NASA Astrophysics Data System (ADS)

    Sakurai, T.; Fujimoto, K.; Matsui, R.; Kawasaki, K.; Okubo, S.; Ohta, H.; Matsubayashi, K.; Uwatoko, Y.; Tanaka, H.

    2015-10-01

    A new piston-cylinder pressure cell for electron spin resonance (ESR) has been developed. The pressure cell consists of a double-layer hybrid-type cylinder with internal components made of the ZrO2-based ceramics. It can generate a pressure of 2 GPa repeatedly and reaches a maximum pressure of around 2.5 GPa. A high-pressure ESR system using a cryogen-free superconducting magnet up 10 T has also been developed for this hybrid-type pressure cell. The frequency region is from 50 GHz to 400 GHz. This is the first time a pressure above 2 GPa has been achieved in multi-frequency ESR system using a piston-cylinder pressure cell. We demonstrate its potential by showing the results of the high-pressure ESR of the S = 1 system with the single ion anisotropy NiSnCl6 · 6H2O and the S = 1 / 2 quantum spin system CsCuCl3. We performed ESR measurements of these systems above 2 GPa successfully.

  19. Electrochemical Aspects of the ESR Process

    NASA Astrophysics Data System (ADS)

    Mitchell, Alec

    2016-07-01

    Current passage in the ESR process is accomplished by at least two Faradaic reaction systems, one at the electrode/slag interface and another at the slag/ingot interface. The nature of these reactions has been investigated and is reported to be a function of the alloy composition, current density and slag composition. In this report, data generated from both DC and line- frequency AC ESR operations is used to relate laboratory investigations on these reactions to results obtained in industrial practice. The operating reaction in the line frequency AC melting of simple alloy steels is found to be principally the reversible anodic oxidation of iron (Fe/Fe2+). In the equivalent DC process there is in addition the cathodic deposition of aluminium, resulting in the formation of substantial amounts of D-type alumina inclusions in the ingot. The Faradaic reactions involve energy exchange which should be taken into account in the process energy balance. They also are likely to change the interface physical characteristics such as interfacial tension. The data is extended to the case of low frequency ESR furnaces in which it is found that the extent of the reactions is strongly dependent on current density. It is concluded that the presence of Faradaic reactions in low frequency furnaces is unlikely to lead to quality problems in the alloys and applications for which these processes are used. This conclusion appears to be supported by industrial practice and leads to a further conclusion that low frequency practices in large ESR furnaces could potentially be replaced by simpler DC systems.

  20. Study of OSL in NaF: Ca,Cu

    NASA Astrophysics Data System (ADS)

    More, Y. K.; Wankhede, S. P.; Moharil, S. V.

    2013-06-01

    Sodium Fluoride containing Cu+ ions was prepared by R.A.P. followed by melt-quenching technique. Results on photo, thermo and optically stimulated luminescence in NaF:Ca,Cu are reported. OSL sensitivity of NaF:Ca,Cu is approximately 2 times than that of standard phosphor LMP. The rate of OSL depletion for 90% decay for NaF:Ca,Cu is 0.3 times as that of OSL phosphor LMP. NaF:Ca,Cu thus deserves much more attention than it has received up till now.

  1. Pulse Dipolar ESR and Protein Superstructures and Function

    NASA Astrophysics Data System (ADS)

    Freed, Jack

    2014-03-01

    Pulse dipolar electron-spin resonance (PDS-ESR) has emerged as a powerful methodology for the study of protein structure and function. This technology, in the form of double quantum coherence (DQC) - ESR and double-electron-electron resonance (DEER) in conjunction with site-directed spin-labeling will be described. It enables the measurement of distances and their distributions in the range of 1-9 nm between pairs of spins labeled at two sites in the protein. Many biological objects can be studied: soluble and membrane proteins, protein complexes, etc. Many sample morphologies are possible: uniform, heterogeneous, etc. thereby permitting a variety of sample types: solutions, liposomes, micelles, bicelles. Concentrations from micromolar to tens of millimolar are amenable, requiring only small amounts of biomolecules. The distances are quite accurate, so a relatively small number of them are sufficient to reveal structures and functional details. Several examples will be shown. The first is defining the protein complexes that mediate bacterial chemotaxis, which is the process whereby cells modulate their flagella-driven motility in response to environmental cues. It relies on a complex sensory apparatus composed of transmembrane receptors, histidine kinases, and coupling proteins. PDS-based models have captured key architectural features of the receptor kinase arrays and the flagellar motor, and their changes in conformation and dynamics that accompany kinase activation and motor switching. Another example will be determining the conformational states and cycling of a membrane transporter, GltPh, which is a homotrimer, in its apo, substrate-bound, and inhibitor-bound, states in membrane vesicles providing insight into its energetics. In a third example the structureless (in solution) proteins alpha-synuclein and tau, which are important in Parkinson's disease and in neurodegeneration will be described and the structures they take on in contact with membranes will be

  2. Characterization of macrosegregation in ESR IN-718

    NASA Technical Reports Server (NTRS)

    Domingue, J. A.; Yu, K. O.; Flanders, H. D.

    1984-01-01

    Aspects of macrosegregation theory, such as dendrite arm spacing, pool profile and mushy zone depth are beneficial to developing consumable melting process for Ion Nickel IN-718, Electro-Slag Refining, especially ESR. Aspects of microsegregation theory, such as correlation of dendrite arm spacing with heat transfer mechanisms and local solidification time, are used to minimize remnant dendritism in both ESR and Vacuum Arc Remelting VAR IN-718. Specifically, ESR IN-718 must be optimized by developing practices which maximize ingot cooling rate and minimize the steepness of the solidus and liquidus isotherms. The knowledge concerning macrosegregation in consumable melted IN-718 is in the form of correlations. Since the isotherm steepness is undoubtedly involved, investigations which include a microgravity environment might separate microsegregation effects from macrosegregation effects. Accounting for the effects of gravity and density differences between the metal pool and the interdendritic fluid, in combination with the pool and mushy zone profiles, can lead to improved melting solidification practices for IN-718, and allow prediction of macrosegregation tendency to be incorporated into high temperature alloy design.

  3. ESR dating of barite in sulphide deposits formed by the sea-floor hydrothermal activities.

    PubMed

    Toyoda, Shin; Fujiwara, Taisei; Uchida, Ai; Ishibashi, Jun-ichiro; Nakai, Shun'ichi; Takamasa, Asako

    2014-06-01

    Barite is a mineral newly found to be practically useful for electron spin resonance (ESR) dating of sulphide deposits formed by the sea-floor hydrothermal activities. The recent studies for the properties of the ESR dating signal in barite are summarised in the present paper as well as the formulas for corrections for accurate dose-rate estimation are developed including the dose-rate conversion factors, shape correction for gamma-ray dose and decay of (226)Ra. Although development of the techniques for ESR dating of barite has been completed, further comparative studies with other dating techniques such as U-Th and (226)Ra-(210)Pb dating are necessary for the technique to be widely used. PMID:24795384

  4. Effects of high-temperature annealing on ESR properties of solid solutions of garnet minerals

    NASA Astrophysics Data System (ADS)

    Gundu Rao, T. K.; Cano, Nilo F.; Chubaci, Jose F. D.; Watanabe, S.

    2016-04-01

    A garnet (G7) silicate mineral belonging to pyralspite subgroup was studied using the technique of electron spin resonance (ESR). This study shows that iron is present in G7 as isolated species as well as species coupled by dipolar interactions. The ESR data shows a gradual increase of cluster of Fe3+ ions accompanied by decrease of dipolar interactions and increase of possible exchange interactions at high temperature. The Fe2+→Fe3+ oxidation process occurs in the garnets as a function of annealing temperature. Thermoluminescence (TL) peaks at approximately 190 and 340 °C are observed in the irradiated G7 garnet. Investigations using the technique of ESR were carried out to identify the centers involved in the TL process.

  5. ESR of copper and iron complexes with antitumor and cytotoxic properties.

    PubMed Central

    Antholine, W E; Kalyanaraman, B; Petering, D H

    1985-01-01

    The relatively few iron and copper metal complexes which have been examined in cells and tissues for their redox properties, radical generation properties, and antitumor activity are discussed for studies which utilized electron spin resonance spectroscopy (ESR). A common property of a number of metal complexes, which include bleomycin, adriamycin, and thiosemicarbazones described in this review, is that they are readily reduced by thiol compounds and oxidized by oxygen or reduced species of oxygen to produce radicals. Structural features of these reactions are identified by ESR spectroscopy in model systems and often in cells. Furthermore, ESR spectroscopy has been most useful to probe the environment of the complexes in cells and to measure the rate of reduction of their oxidized forms. As a result of these studies, it is anticipated that more attention will be given to the exploration of redox-active metal complexes as drugs. PMID:2420582

  6. Comparative cavitation erosion test on steels produced by ESR and AOD refining

    NASA Astrophysics Data System (ADS)

    Dojčinović, M.

    2011-09-01

    Cavitation erosion studies of steels produced by Electroslag Refining (ESR) and Argon Oxygen Decarburization (AOD refining) have been carried out. The experiments were conducted using the modified ultrasonically induced cavitation test method. Erosion rates were measured and the morphology of damages under cavitation action was studied by scanning electron microscopy and optical microscopy techniques. The present work is aimed at understanding the cavitation erosion behaviour of electroslag refined steel (ESR) compared with the steel produced by Argon Oxygen Decarburization (AOD refining), commonly used in the production of hydraulic machinery parts (Pelton blades). The results exhibited lower cavitation rate of ESR steel compared with AOD steel, as a consequence of its better mechanical properties and homogeneous and fine-grained microstructure.

  7. Positron lifetime studies of decomposition in 2024 (Al-Cu-Mg) and 7010 (Al-Zn-Cu-Mg) alloys

    SciTech Connect

    Dlubek, G. |; Lademann, P.; Krause, H.; Krause, S.; Unger, R.

    1998-09-04

    In the current paper, the decomposition behavior of the engineering alloys 2024 (Al-Cu-Mg) and 7010 (Al-Zn-Cu-Mg) is studied using positron lifetime measurements. Positrons probe open volume defects such as vacancies and dislocations. However, they may also be used to investigate coherent zones and incoherent precipitates. In order to understand the rather complicated precipitation sequences and the response of positrons to different type of precipitates occurring in 2024 and 7010 alloys, binary and ternary laboratory alloys were also investigated under the same experimental conditions as the engineering alloys. The interpretations of the results are based on experiences of the group from extensive positron studies of laboratory alloys such as Al-Zn, Al-Zn-Mg, Al-Cu, and further Al alloys (see also the review (4)). Their collected results are shown as lifetimes and curve-shape parameters S of the electron-positron momentum distribution curves characteristic for different precipitates in Al alloys.

  8. First-principles study for ferromagnetism of Cu-doped ZnO with carrier doping

    SciTech Connect

    Kang, Byung-Sub; Kim, Kyeong-Sup; Yu, Seong-Cho; Chae, Heejoon

    2013-02-15

    We studied the effects on the ferromagnetism of carrier doping in Zn{sub 1-x}Cu{sub x}O with x=0.0277-0.0833 by using the first-principles calculations. The total magnetic moment of Cu is about 1, 2, and 3 {mu}{sub B}/cell at the concentration of 2.77%, 5.55%, and 8.33%, respectively. For Zn{sub 1-x}Cu{sub x}O{sub 1-y}N{sub y}, we obtained the ferromagnetic and half-metallic ground state. The Cu magnetic moment in low Cu concentration is increased by the N-doping. However, for the F-doping it decreases. The ferromagnetism in Cu-doped ZnO is controllable by changing the carrier density. The N 2p states hybridize well with Cu 3d states instead of the O 2p states. Due to the hybridization between N 2p and Cu 3d states, the holes are itinerant with keeping its 3d states. For (Cu,N)-codoped ZnO, it is recognized that the width of 3d states is larger than that of (Cu,F)-codoped ZnO. - Graphical abstract: Considered clean wurtzite ZnO structure, the Cu magnetic moments for Zn{sub 1-x}Cu{sub x}O{sub 1-y}N{sub y} or Zn{sub 1-x}Cu{sub x}O{sub 1-y}F{sub y} of the ferromagnetic state (left), and the charge density difference of Zn{sub 1-x}Cu{sub x}O (x=0.0277) (right). Highlights: Black-Right-Pointing-Pointer The ferromagnetism of Cu-doped ZnO is controllable by N or F carrier density. Black-Right-Pointing-Pointer The Cu magnetic moment in low Cu concentration is increased by hole doping. Black-Right-Pointing-Pointer The N 2p states hybridize well with the Cu 3d states instead of the O 2p states. Black-Right-Pointing-Pointer For (Cu,F)-codoped ZnO, the Cu 3d band is narrower than that for (Cu,N)-codoped ZnO.

  9. ESR and Microwave Absorption in Boron Doped Diamond Single Crystals

    NASA Astrophysics Data System (ADS)

    Timms, Christopher

    2015-03-01

    Superconductivity has been reportedly found in boron-doped diamond. Most research to date has only studied superconductivity in polycrystalline and thin film boron-diamonds, as opposed to a single crystal. In fact, only one other group has examined a macro scale boron-doped diamond crystal. Our group has successfully grown large single crystals by using the High Temperature High Pressure method (HTHP) and observed a transition to metallic and superconducting states for high B concentrations. For the present, we are studying BDD crystal using Electron Spin Resonance. We conducted our ESR analysis over a range of temperatures (2K to 300K) and found several types of signals, proving the existence of charge carriers with spin 1/2 in BDD. Moreover, we have found that with increasing B concentrations, from n ~ 1018 cm-3 to n of over 1020 cm-3, the ESR signal changes from that of localized spins to the Dysonian shape of free carriers. The low magnetic field microwave absorption has also been studied in BDD samples at various B concentrations and the clear transition to superconducting state has been found below Tc that ranges from 2K to 4 K depending on concentration and quality of crystal. Sergey Polyakov, Victor Denisov, Vladimir Blank, Ray Baughman, Anvar Zakhidov.

  10. ESR response of phenol compounds for dosimetry of gamma photon beams

    NASA Astrophysics Data System (ADS)

    Marrale, M.; Longo, A.; Panzeca, S.; Gallo, S.; Principato, F.; Tomarchio, E.; Parlato, A.; Buttafava, A.; Dondi, D.; Zeffiro, A.

    2014-11-01

    In the present paper we investigate the features of IRGANOX® 1076 phenols as a material for electron spin resonance (ESR) dosimetry. We experimentally analyzed the ESR response of pellets of IRGANOX® 1076 phenols irradiated with 60Co photons. The best experimental parameters (modulation amplitude and microwave power) for dosimetric applications have been obtained. The dependence of ESR signal as function of γ dose is found to be linear in the dose range studied (12-60 Gy) and the lowest measurable dose is found to be of the order of 1 Gy. The signal after irradiation is very stable in the first thirty days. From the point of view of the tissue equivalence, these materials have mass energy absorption coefficient values comparable with those of soft tissue.

  11. Effect of doping LiMn2O4 spinel with a tetravalent species such as Si(IV) versus with a trivalent species such as Ga(III). Electrochemical, magnetic and ESR study

    NASA Astrophysics Data System (ADS)

    Iturrondobeitia, A.; Goñi, A.; Palomares, V.; Gil de Muro, I.; Lezama, L.; Rojo, T.

    2012-10-01

    Three cathode compounds for lithium ion batteries, LiMn2O4, LiMn1.95Si0.05O4 and LiMn1.9Ga0.1O4 have been synthesized by the freeze-drying method. All samples present partially sintered particles of 80 nm average size, corresponding to single crystalline phases with cubic spinel structure. The substitution of a little portion of Mn(IV) by Si(IV) in the crystal framework leads to more expanded and regular MnO6 octahedra, whereas the replacement of some Mn(III) by Ga(III) induces the opposing effect. The ESR measurements support the effectiveness of doping as an evolution of the width of the resonance signal with the composition is observed. A complete magnetic study has been carried out, including ac and dc magnetic susceptibility measurements at different fields, FC and ZFC, and magnetization versus field. Due to the in-built magnetic frustration in spinel structure and the competition between different exchange pathways, the insertion of small quantities of dopants causes significant differences in the magnetic behaviour. The electrochemical study has revealed very good values of specific capacity for LiMn1.95Si0.05O4 reaching 146 mA h g-1 and 139 mA h g-1 at C/10 and 1C rates, respectively. A capacity retention up to 75% has been observed for the three samples after 300th cycles.

  12. Synthesis, spectral characterization and antioxidant activity studies of a bidentate Schiff base, 5-methyl thiophene-2-carboxaldehyde-carbohydrazone and its Cd(II), Cu(II), Ni(II) and Zn(II) complexes

    NASA Astrophysics Data System (ADS)

    Harinath, Y.; Harikishore Kumar Reddy, D.; Naresh Kumar, B.; Apparao, Ch.; Seshaiah, K.

    2013-01-01

    A new Schiff base bidentate ligand (L), 5-methyl thiophene-2-carboxaldehyde-carbohydrazone and its metal (Cu(II), Cd(II), Ni(II) and Zn(II)) complexes with general stoichiometry [M(L)2X2] (where X = Cl) were synthesized. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H NMR, ESR spectral analyses, and molar conductance studies. The molar conductance data revealed that all the metal chelates are non-electrolytes. IR spectra showed that ligand (L) is coordinated to the metal ions in a bidentate manner with N and O donor sites of the azomethine-N, and carbonyl-O. ESR and UV-Vis spectral data showed that the geometrical structure of the complexes are Orthorhombic. Furthermore, the antioxidant activity of the ligand and its complexes was determined by hydroxyl radical scavenging, DPPH, NO, reducing power methods in vitro. The obtained IC50 value of the DPPH activity for the copper complex (IC50 = 66.4 μm) was higher than other compounds. Microbial assay of the above complexes against Staphylococcus aureus, Escherichia coli, Rhizocotonia bataticola and Alternaria alternata showed that copper complex exhibited higher activity than the other complexes.

  13. Photoluminescence Studies in CuAlS2 Crystals

    NASA Astrophysics Data System (ADS)

    Shirakata, Sho; Aksenov, Igor; Sato, Katsuaki; Isomura, Shigehiro

    1992-08-01

    Photoluminescence (PL) measurements have been carried out at low temperature (77 and 10 K) on CuAlS2 crystals grown by the chemical vapor transport method. Seven sharp PL lines have been observed near the band edge. Based on the photoreflectance measurements, the PL line at 3.550 eV has been assigned to a free exciton emission. The lines at 3.540, 3.532, 3.500 and 3.475 eV are tentatively assigned to the bound excitons, and they are discussed in terms of the crystal composition and the annealing conditions. This study also refers to the PL lines and peaks at about 2.9 eV.

  14. Incidence and clinical significance of ESR1 mutations in heavily pretreated metastatic breast cancer patients

    PubMed Central

    Niu, Jiaxin; Andres, Grant; Kramer, Kim; Kundranda, Madappa N; Alvarez, Ricardo H; Klimant, Eiko; Parikh, Ankur R; Tan, Bradford; Staren, Edgar D; Markman, Maurie

    2015-01-01

    Background ESR1 mutation has recently emerged as one of the important mechanisms involved in endocrine resistance. The incidence and clinical implication of ESR1 mutation has not been well evaluated in heavily pretreated breast cancer patients. Methods We conducted a retrospective review of advanced breast cancer patients with tumors who underwent next-generation sequencing genomic profiling using Foundation One test at Cancer Treatment Centers of America® regional hospitals between November 2012 and November 2014. Results We identified a total of 341 patients including 217 (59%) estrogen receptor (ER)+, 177 (48%) progesterone receptor (PR)+, 30 (8%) hormone receptor+/HER2 positive, and 119 (32%) triple negative patients. ESR1 mutation was noted in 27/222 (12.1%) ER+ or PR+ breast cancer patients. All ER+ patients received at least one line of an aromatase inhibitor. All 28 patients were found to harbor ESR1 mutations affecting ligand-binding domain with the most common mutations affecting Y537 (17/28, 60.7%) and D538 (9/28, 32.1%). In this cohort, 19 (67.9%) patients carried three or more, seven (25%) patients had one or two additional genomic alterations and one (3.6%) patient had an ESR1 mutation only. Of 28 patients, three patients were treated with fulvestrant immediately before and two patients were treated after next-generation sequencing testing; only one patient achieved stable disease for 8 months and the other four patients had progression of disease. In all, 3/3 (100%) patients before testing and 2/4 (50%) after testing treated with exemestane and everolimus achieved stable disease for at least 6 months. Conclusion ESR1 mutation was found in 12.1% of a large cohort of advanced breast cancer patients. Exemestane in combination with everolimus might be a reasonable option. Prospective studies are warranted to validate these findings. PMID:26648736

  15. Impact of ESR1 Gene Polymorphisms on Migraine Susceptibility

    PubMed Central

    Li, Li; Liu, Ruozhuo; Dong, Zhao; Wang, Xiaolin; Yu, Shengyuan

    2015-01-01

    Abstract An increasing number of studies have explored genetic associations between the functionally important polymorphisms in estrogen receptor 1 (ESR1) gene and migraine susceptibility. The previously reported associations have nevertheless been inconsistent. The present work incorporating the published data derived from 8 publications was performed to assess the impact of these polymorphisms on incident migraine. Strength of the genetic risk was estimated by means of an odds ratio along with the 95% confidence interval (OR and 95% CI). From the results, we found individuals who harbored the 325-GG genotype, compared with those harboring the CC genotype or CG and CC combined genotypes, had almost 50% greater risk of migraine. The same genetic models showed notable associations in subgroups of Caucasians and migraine with aura (MA). For 594G>A, a moderately increased risk of migraine was seen under AG versus GG. The AA + AG versus GG model, however, showed a borderline association with migraine. Subgroup analyses according to ethnicity and subtype of migraine provided statistical evidence of significantly increased risk of migraine in Caucasians and of a marginal association with MA, respectively. Both 325C>G and 594G>A polymorphisms showed no major effects either in males or in females. Based on the statistical data, we conclude some of the ESR1 gene polymorphisms may have major contributions to the pathogenesis of migraine in Caucasian populations. PMID:26334887

  16. Co(II), Cu(II), Cd(II), Fe(III) and U(VI) complexes containing a NSNO donor ligand: Synthesis, characterization, optical band gap, in vitro antimicrobial and DNA cleavage studies

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; Abu El-Reash, G. M.; El-Gammal, O. A.; Bedier, R. A.

    2012-12-01

    A new series of [Co(HPTP)Cl(H2O)2], [Cu(HPTP)Cl], [Cd(HPTP)Cl](H2O)4, [Fe(PTP)Cl(H2O)2](H2O), [UO2(HPTP)(OAc)(H2O)2] complexes of Schiff-bases derived from 4-(2-pyridyl)-3-thiosemicarbazide and pyruvic acid (H2PTP) have been synthesized and characterized by spectroscopic studies. Schiff-base exhibit thiol-thione tautomerism wherein sulfur plays an important role in the coordination. The coordination possibility of the Schiff-bases towards metal ions have been proposed in the light of elemental analyses, spectral (IR, UV-vis, 1H NMR, 13C NMR and ESR), magnetic and thermal studies. IR spectra show that H2PTP is coordinated to the metal ions in a mono or binegative tridentate manner. The electronic spectra of the complexes and their magnetic moments provide information about geometries. The room temperature solid state ESR spectra of the Cu(II) complexes show dx2-y2 as a ground state, suggesting square-planar geometry around Cu(II) center. The molecular parameters: total energy, binding energy, isolated atomic energy, electronic energy, heat of formation, dipole moment, HOMO and LUMO were calculated for the ligand and its complexes. Furthermore, the kinetic and thermodynamic parameters for the different decomposition steps were calculated using the Coats-Redfern and Horowitz-Metzger methods. Also, the optical band gap (Eg) of the metal complexes has been calculated. The optical transition energy (Eg) is direct and equals 3.25, 3.26, 3.34 and 3.27 eV for Co, Cu, Fe and U complexes, respectively. The synthesized ligand, in comparison to its metal complexes is screened for its antibacterial activity against bacterial species, Bacillus thuringiensis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli. The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species. Finally, the biochemical studies showed that, Cu, Cd and Fe complexes have powerful and complete

  17. Synthesis, spectral, antitumor, antioxidant and antimicrobial studies on Cu(II), Ni(II) and Co(II) complexes of 4-[(1H-Benzoimidazol-2-ylimino)-methyl]-benzene-1,3-diol

    NASA Astrophysics Data System (ADS)

    El-wakiel, Nadia; El-keiy, Mai; Gaber, Mohamed

    2015-08-01

    A new Schiff base of 2-aminobenzimidazole with 2,4-dihydroybezaldehyde (H3L), and its Cu(II), Ni(II) and Co(II) complexes have been synthesized and characterized by elemental analyses, molar conductance, thermal analysis (TGA), inductive coupled plasma (ICP), magnetic moment measurements, IR, EI-mass, UV-Vis. and ESR spectral studies. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as dibasic tridentate ligand coordinating via deprotonated OH, NH and azomethine nitrogen atom. The results showed that Co(II) and Ni(II) complexes have tetrahedral structure while Cu(II) complexes has octahedral geometry. The kinetic and thermodynamic parameters of the thermal decomposition stages have been evaluated. The studied complexes were tested for their in vitro antimicrobial activities against some bacterial strains. The anticancer activity of the ligand and its metal complexes is evaluated against human liver Carcinoma (HEPG2) cell. These compounds exhibited a moderate and weak activity against the tested HEPG2 cell lines with IC50 of 9.08, 18.2 and 19.7 μg/ml for ligand, Cu(II) and Ni(II) complexes, respectively. In vitro antioxidant activity of the newly synthesized compounds has also been evaluated.

  18. Low-Temperature Studies of CuFe2 S3 and CuFeS2 by ^{63,65} Cu NMR in the Internal Magnetic Field

    NASA Astrophysics Data System (ADS)

    Gavrilenko, Andrey Nikolaevich; Pogoreltsev, Aleksandr Iliich; Matukhin, Vadim Leonidovich; Korzun, Barys Vasilyevich; Schmidt, Ekaterina Vadimovna; Sevastianov, Iliya Germanovich

    2016-02-01

    The resonance ^{63,65} Cu NMR spectra in the internal magnetic field in cubanite CuFe2 S3 and chalcopyrite CuFeS2 were studied experimentally at 77 K. Using a cluster approach, ab initio evaluation of the electric field gradient (EFG) at the nuclei of copper in both compounds was performed. The calculations were carried out by the self-consistent restricted method of Hartree-Fock with open shells (SCF-LCAO-ROHF). The largest clusters for which calculations were made had a formula of Cu7 Fe_{14} S_{29}^n for cubanite and Cu9 Fe_{10} S_{28}^n for chalcopyrite, where n is the cluster charge. The best-fit values of the quadrupole parameters (quadrupole frequency ν _Q and the asymmetry parameter of the EFG tensor η )—determined experimentally (ν _Q ≈ 7.30 MHz and η ≈ 0.82) and by calculation (ν _Q ≈ 7.38 MHz and η ≈ 0.87)—were obtained for a cluster Cu7 Fe_{14} S_{29}^{10} for cubanite. Similarly, the best-fit values of the quadrupole parameters—determined experimentally (ν _Q ≈ 1.29 MHz and η ≈ 0.34) and by calculation (ν _Q ≈ 1.40 MHz and η ≈ 0.50)—were obtained for a cluster Cu9 Fe_{10} S_{28}^{-4} for chalcopyrite. For these clusters, maps of the electron density distribution in the neighborhood of quadrupole nucleus of copper were built. Based on the analysis of the resulting electron density distribution, it is supposed that the bond in these compounds is not quite covalent. Evaluations of the hyperfine interaction constants were made and maps of the spin density distribution in the neighborhood of quadrupole nucleus of copper were built. The energy level diagram calculated in the high-spin ROHF approximation defined chalcopyrite as a compound with a very narrow LUMO-HOMO gap rather well and is consistent with the notion of this compound as a semiconductor.

  19. Study of Cu and Pb partitioning in mine tailings using the Tessier sequential extraction scheme

    NASA Astrophysics Data System (ADS)

    Andrei, Mariana Lucia; Senila, Marin; Hoaghia, Maria Alexandra; Borodi, Gheorghe; Levei, Erika-Andrea

    2015-12-01

    The Cu and Pb partitioning in nonferrous mine tailings was investigated using the Tessier sequential extraction scheme. The contents of Cu and Pb found in the five operationally defined fractions were determined by inductively coupled plasma optical emission spectrometry. The results showed different partitioning patterns for Cu and Pb in the studied tailings. The total Cu and Pb contents were higher in tailings from Brazesti than in those from Saliste, while the Cu contents in the first two fractions considered as mobile were comparable and the content of mobile Pb was the highest in Brazesti tailings. In the tailings from Saliste about 30% of Cu and 3% of Pb were found in exchangeable fraction, while in those from Brazesti no metals were found in the exchangeable fraction, but the percent of Cu and Pb found in the bound to carbonate fraction were high (20% and 26%, respectively). The highest Pb content was found in the residual fraction in Saliste tailings and in bound to Fe and Mn oxides fraction in Brazesti tailings, while the highest Cu content was found in the fraction bound to organic matter in Saliste tailings and in the residual fraction in Brazesti tailings. In case of tailings of Brazesti medium environmental risk was found both for Pb and Cu, while in case of Saliste tailings low risk for Pb and high risk for Cu were found.

  20. An EELS study of Cu adsorbed on O/W(110) and CO/W(110)

    NASA Astrophysics Data System (ADS)

    Houston, J. E.; O'Neill, D. G.; Gomer, R.

    1991-03-01

    The vibrational properties of 1 monolayer of Cu adsorbed on O/W(110), Cu 1/O/W(110), O/Cu 1/W(110) and Cu 1-1.5/CO/W(110) were studied at 90 K and on heating to see if the existence of sandwich structures and the electric shielding by single metal layers suggested by previous work [N. Shamir, J.C. Lin and R. Gomer, J. Chem. Phys. 90 (1989) 5135] could be confirmed. It was found that a monolayer of Cu screens the OW dipole moment effectively while 1.5 Cu monolayers were required for CO on W, probably because in that case a continuous Cu layer is not formed. It was also found that heating Cu 1/O/W(110) and O/CU 1W(110) layers gave results which support previous findings on OCu segregation [J.S. Lin, N. Shamir and R. Gomer, Surf. Sci. 206 (1988) 206].

  1. Study of Cu and Pb partitioning in mine tailings using the Tessier sequential extraction scheme

    SciTech Connect

    Andrei, Mariana Lucia; Senila, Marin; Hoaghia, Maria Alexandra; Levei, Erika-Andrea; Borodi, Gheorghe

    2015-12-23

    The Cu and Pb partitioning in nonferrous mine tailings was investigated using the Tessier sequential extraction scheme. The contents of Cu and Pb found in the five operationally defined fractions were determined by inductively coupled plasma optical emission spectrometry. The results showed different partitioning patterns for Cu and Pb in the studied tailings. The total Cu and Pb contents were higher in tailings from Brazesti than in those from Saliste, while the Cu contents in the first two fractions considered as mobile were comparable and the content of mobile Pb was the highest in Brazesti tailings. In the tailings from Saliste about 30% of Cu and 3% of Pb were found in exchangeable fraction, while in those from Brazesti no metals were found in the exchangeable fraction, but the percent of Cu and Pb found in the bound to carbonate fraction were high (20% and 26%, respectively). The highest Pb content was found in the residual fraction in Saliste tailings and in bound to Fe and Mn oxides fraction in Brazesti tailings, while the highest Cu content was found in the fraction bound to organic matter in Saliste tailings and in the residual fraction in Brazesti tailings. In case of tailings of Brazesti medium environmental risk was found both for Pb and Cu, while in case of Saliste tailings low risk for Pb and high risk for Cu were found.

  2. In-place ESR microwave conductivity measurements and electronic band structure studies of the organic superconductor {beta}{double_prime}-(BEDT-TTF){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3}

    SciTech Connect

    Wang, H.H.; VanZile, M.L.; Schlueter, J.A.

    1999-07-01

    The electronic structure of the organic superconductor {beta}{double_prime}-(BEDT-TTF){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3} (BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene) was characterized with the use of electron spin resonance (ESR) spectroscopy and electronic band structure calculations. The room-temperature ESR line width is 24--27 G in the plane of a donor molecule layer (i.e., in the ab-plane) and {approximately} 32 G along the normal to this plane (i.e., along the c*-direction). The ab-plane anisotropy of the microwave conductivity was extracted for the first time from the ESR Dysonian line shape analysis. The in-plane conductivity varies sinusoidally, is maximal along the interstack direction (b-axis), and is minimal along the donor stack direction ({alpha}-axis). The Fermi surfaces of the title compound consist of a 2D hole pocket and a pair of 1D wavy lines. The directions for the in-plane conductivity maximum and minimum are in excellent agreement with the electronic band structure calculated for {beta}{double_prime}-(BEDT-TTF){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3}, and the origin of the in-plane conductivity anisotropy lies in the one-dimensional part of the Fermi surface. This is the first time that an organic conductor shows Dysonian ESR line shape due to its 2D and strongly metallic nature, yet the 1D character is revealed simultaneously through the in-plane conductivity anisotropy.

  3. In-plane ESR microwave conductivity measurements and electronic band structure studies of the organic superconductor, {beta}'-(BEDT-TTF){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3}.

    SciTech Connect

    Wang, H. H.; VanZile, M. L.; Schlueter, J. A.; Geiser, U.; Kini, A. M.; Sche, P. P.; Koo, H.-J.; Whangbo, M.-H.; Nixon, P. G.; Winter, R. W.; Gard, G. L.; Chemistry; North Carolina State Univ.; Portland State Univ.

    1999-07-01

    The electronic structure of the organic superconductor {beta}''-(BEDT-TTF){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3} (BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene) was characterized with the use of electron spin resonance (ESR) spectroscopy and electronic band structure calculations. The room-temperature ESR line width is 24-27 G in the plane of a donor molecule layer (i.e., in the ab-plane) and {approx}32 G along the normal to this plane (i.e., along the c*-direction). The ab-plane anisotropy of the microwave conductivity was extracted for the first time from the ESR Dysonian line shape analysis. The in-plane conductivity varies sinusoidally, is maximal along the interstack direction (b-axis), and is minimal along the donor stack direction (a-axis). The Fermi surfaces of the title compound consist of a 2D hole pocket and a pair of 1D wavy lines. The directions for the in-plane conductivity maximum and minimum are in excellent agreement with the electronic band structure calculated for {beta}''-(BEDT-TTF){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3}, and the origin of the in-plane conductivity anisotropy lies in the one-dimensional part of the Fermi surface. This is the first time that an organic conductor shows Dysonian ESR line shape due to its 2D and strongly metallic nature, yet the 1D character is revealed simultaneously through the in-plane conductivity anisotropy.

  4. EPR Study of [Cu(Him)4]·2Br Complex

    NASA Astrophysics Data System (ADS)

    Yıldırım, İ.; Karabulut, B.

    2016-04-01

    The single crystal of [Cu(Him)4]·2Br (Him: C3H4N2, imidazole) complex has been investigated at ambient temperature in three mutually perpendicular planes by EPR technique. The magnetic environments of [Cu(Him)4]·2Br complex have been identified by EPR technique. The study reveals the existence of two magnetically inequivalent Cu2+ sites. The principal values of g tensors were obtained. The EPR parameters show that the paramagnetic centers have rhombic symmetry.

  5. Gamma radiation effects on seed germination, growth and pigment content, and ESR study of induced free radicals in maize (Zea mays).

    PubMed

    Marcu, Delia; Damian, Grigore; Cosma, Constantin; Cristea, Victoria

    2013-09-01

    The effects of gamma radiation are investigated by studying plant germination, growth and development, and biochemical characteristics of maize. Maize dry seeds are exposed to a gamma source at doses ranging from 0.1 to 1 kGy. Our results show that the germination potential, expressed through the final germination percentage and the germination index, as well as the physiological parameters of maize seedlings (root and shoot lengths) decreased by increasing the irradiation dose. Moreover, plants derived from seeds exposed at higher doses (≤0.5 kGy) did not survive more than 10 days. Biochemical differences based on photosynthetic pigment (chlorophyll a, chlorophyll b, carotenoids) content revealed an inversely proportional relationship to doses of exposure. Furthermore, the concentration of chlorophyll a was higher than chlorophyll b in both irradiated and non-irradiated seedlings. Electron spin resonance spectroscopy used to evaluate the amount of free radicals induced by gamma ray treatment demonstrates that the relative concentration of radiation-induced free radicals depends linearly on the absorbed doses. PMID:23996407

  6. Are the current theories of electron transfer applicable to reactions in ionic liquids? An ESR-study on the TCNE/TCNE(-)˙ couple.

    PubMed

    Mladenova, B Y; Kattnig, D R; Sudy, B; Choto, P; Grampp, G

    2016-05-25

    Chemical reactivity is profoundly affected by solvent properties. Room temperature ionic liquids (RTILs) obtain molecular environments that differ vastly from those established using molecular solvents with comparable macroscopic properties. In particular, charges are expected to be completely shielded in RTILs even though their dielectric constants are typically low. This raises the question whether electron transfer (ET) reactions in RTILs can be described in terms of Marcus' theory, a model that is fundamentally based on continuum dielectric theory. Herein, we elucidate this question by studying a degenerate electron transfer process, which by design, is not affected by ambiguities in the driving force of the reaction and thus allows a clear-cut assessment of the ET activation energy. We report the rate constants and the activation parameters of the electron self-exchange reaction in the TCNE/TCNE˙(-) couple in seven ionic liquids. The exchange rate constants range from 5.4 × 10(7) M(-1) s(-1) to 9.1 × 10(8) M(-1) s(-1) at 330 K and the activation energies vary from 14 kJ mol(-1) to 41 kJ mol(-1). The results are discussed in the framework of Marcus' theory. It is found that the solvent dependence of the rate constants cannot be described by the classical proportionality to the Pekar factor γ = (1/n(2) - 1/εs). PMID:27171365

  7. Application of high resolution NMR, ESR, and gamma-ray scintillation spectroscopy to the study of ligand binding in proteins. [Torpedo californica

    SciTech Connect

    Lancione, G.V.

    1982-01-01

    Electron spin resonance spectroscopy has been employed to study the nature of the ligand binding site of alpha-1-antitrypsin. Spectra of spin-labeled alpha-1-antitrypsin were recorded at pH's ranging from 2.4 to 12.5. This data demonstrates the tight binding of the spin-label to the protease, and the sensitivity of the bound spin-label to informational changes in the protease inhibitor. A molecular dipstick approach has also been applied to this system and has yielded information on the geometry of the cleft accommodating the spin-label. /sup 160/Terbium(III) exchange experiments have been performed on the acetylcholine receptor protein isolated from Torpedo californica, employing a specially designed flow dialysis apparatus constructed in the laboratory. The apparatus is designed to allow continuous monitoring of /sup 160/Tb(III) gamma-ray emission from the protein compartment of the flow dialysis cell. Nicotinic ligand-induced displacement of /sup 160/Tb(III) from the nicotinic binding site of the receptor was monitored as a funtion of (1) the concentration of nicotinic ligand in the washout buffer, and (2) the nature of the nicotinic ligand in the buffer. Measured /sup 160/Tb(III) exchange half-lives indicate (1) a direct relationship between /sup 160/Tb(III) displacement and nicotinic ligand concentration in the wash-out buffer, and (2) an enhanced /sup 160/Tb(III) displacement for nicotinic agents possessing quaternary ammonium functions.

  8. NMR and ESR characterization of activated carbons produced from pecan shells

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A large number of solid-state NMR and ESR experiments were explored as potential tools to study chemical structure, mobility, and pore volume of activated carbon. We used a model system where pecan shells were activated with phosphoric acid, and carbonized at 450ºC for 4 h with varying amounts of ai...

  9. Raman scattering studies of Cu2ZnSnS4 thin films: Local distribution of the secondary phase Cu2- x S and the effect of KCN etching on Cu2- x S

    NASA Astrophysics Data System (ADS)

    Nguyen, Trang Thi Thu; Shin, Hae-Young; Kim, Gee Yeong; Kim, Ju Ri; Jo, William; Yoon, Seokhyun; Lee, Ki Doo; Kim, Jin Young

    2015-01-01

    We used X-ray diffraction (XRD) and Raman scattering spectroscopy to study Cu2ZnSnS4 (CZTS) thin films grown by using an electroplating method. We compared the Raman spectra of the CZTS thin films before and after potassium cyanide (KCN) etching. We observed a phonon mode of the secondary phase Cu2- x S both from Cu-rich and Cu-poor CZTS samples before the KCN etching. We found that the intensity of the Cu2- x S-related vibration mode depended on the excitation wavelength, from which we could estimate the stoichiometry of the Cu2- x S as x = 1. Interestingly, the Cu2- x S phonon is completely removed after the KCN etching. We could also get information regarding the local distribution of the secondary phase on the surfaces of the CZTS thin films by using micro-Raman scattering spectroscopy.

  10. ESR Studies of a Reorienting Nickel Complex

    NASA Astrophysics Data System (ADS)

    Kowert, Bruce

    2007-03-01

    Electron spin resonance spectra of the planar bis(maleonitriledithiolato)nickel anion radical (BMNT) in the intermediate motional region have been simulated in several polar solvents using axially symmetric reorientation. The rotational diffusion about the long in-plane axis is three to four times faster than that about the two axes perpendicular to it. The reorientational model needed to produce agreement with experiment is either in or close to the Brownian rotational diffusion limit. The solvents are 4-allyl-2-methoxyphenol (eugenol), dimethyl phthalate, tri-n-butyl phosphate, tris(2-ethyl-hexyl)phosphate, and 2-methoxyethyl ether (diglyme), ethyl alcohol, and a dimethylformamide-chloroform mixed solvent. The reorientational rates from the simulations are in general agreement with those from line width analyses carried out from the fast to the slow motional regions. The temperature dependence of the diffusion rates is discussed in terms of the Stokes-Einstein-Debye (SED) model and the Vogel-Tammann-Fulcher equation.

  11. DNA cleavage, antimicrobial, spectroscopic and fluorescence studies of Co(II), Ni(II) and Cu(II) complexes with SNO donor coumarin Schiff bases

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Naik, Vinod H.; Kulkarni, Ajaykumar D.; Badami, Prema S.

    2010-01-01

    A series of Co(II), Ni(II) and Cu(II) complexes of the type ML 2 have been synthesized with Schiff bases derived from methylthiosemicarbazone and 5-formyl-6-hydroxy coumarin/8-formyl-7-Hydroxy-4-methylcoumarin. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMF indicate that, the complexes are non-electrolytes in nature. In view of analytical, spectral (IR, UV-vis, ESR, FAB-mass and fluorescence), magnetic and thermal studies, it has been concluded that, all the metal complexes possess octahedral geometry in which ligand is coordinated to metal ion through azomethine nitrogen, thione sulphur and phenolic oxygen atom via deprotonation. The redox behavior of the metal complexes was investigated by using cyclic voltammetry. The Schiff bases and their complexes have been screened for their antibacterial ( Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi) and antifungal activities ( Aspergillus niger, Aspergillus flavus and Cladosporium) by Minimum Inhibitory Concentration method. The DNA cleavage is studied by agarose gel electrophoresis method.

  12. The use of ESR technique for assessment of heating temperatures of archaeological lentil samples

    NASA Astrophysics Data System (ADS)

    Aydaş, Canan; Engin, Birol; Dönmez, Emel Oybak; Belli, Oktay

    2010-01-01

    Heat-induced paramagnetic centers in modern and archaeological lentils ( Lens culinaris, Medik.) were studied by X-band (9.3 GHz) electron spin resonance (ESR) technique. The modern red lentil samples were heated in an electrical furnace at increasing temperatures in the range 70-500 °C. The ESR spectral parameters (the intensity, g-value and peak-to-peak line width) of the heat-induced organic radicals were investigated for modern red lentil ( Lens culinaris, Medik.) samples. The obtained ESR spectra indicate that the relative number of heat-induced paramagnetic species and peak-to-peak line widths depends on the temperature and heating time of the modern lentil. The g-values also depend on the heating temperature but not heating time. Heated modern red lentils produced a range of organic radicals with g-values from g = 2.0062 to 2.0035. ESR signals of carbonised archaeological lentil samples from two archaeological deposits of the Van province in Turkey were studied and g-values, peak-to-peak line widths, intensities and elemental compositions were compared with those obtained for modern samples in order to assess at which temperature these archaeological lentils were heated in prehistoric sites. The maximum temperatures of the previous heating of carbonised UA5 and Y11 lentil seeds are as follows about 500 °C and above 500 °C, respectively.

  13. Magnetic-Field-Induced Low-Energy Spin Excitations in YBa2Cu4O8 Measured by High Field Gd3+ Electron Spin Resonance

    NASA Astrophysics Data System (ADS)

    Fehér, Titusz; Jánossy, András; Oszlányi, Gábor; Simon, Ferenc; Dabrowski, Bogdan; Klamut, Piotr W.; Horvatić, Mladen; Williams, Grant V.

    2000-12-01

    We have measured the spin susceptibility, χs, of the CuO2 planes in the underdoped high Tc superconductor, YBa2Cu4O8 by Gd3+ electron spin resonance (ESR) in single crystals and aligned powders in fields up to 15.4 T. At low temperatures and high fields, χs is enhanced slightly in the B∥c orientation with respect to the B⊥c orientation. The enhancement at 15.4 T ( ~0.15Hc2) at 16 K ( 0.2 Tc) is small: approximately 10% of χs\\(Tc\\), suggesting that the second critical field of superconductivity, Hc2~100 T, would not suppress the pseudogap. This work demonstrates the potential of high field ESR in single crystals for studying high Tc superconductors.

  14. First-principles study of carbon impurities in CuInSe{sub 2} and CuGaSe{sub 2}, present in non-vacuum synthesis methods

    SciTech Connect

    Bekaert, J. Saniz, R.; Partoens, B.; Lamoen, D.

    2015-01-07

    A first-principles study of the structural and electronic properties of carbon impurities in CuInSe{sub 2} and CuGaSe{sub 2} is presented. Carbon is present in organic molecules in the precursor solutions used in non-vacuum growth methods for CuInSe{sub 2} and CuGaSe{sub 2} based photovoltaic cells. These growth methods make more efficient use of material, time, and energy than traditional vacuum methods. The formation energies of several carbon impurities are calculated using the hybrid HSE06 functional. C{sub Cu} acts as a shallow donor, C{sub In} and interstitial C yield deep donor levels in CuInSe{sub 2}, while in CuGaSe{sub 2} C{sub Ga} and interstitial C act as deep amphoteric defects. So, these defects reduce the majority carrier (hole) concentration in p-type CuInSe{sub 2} and CuGaSe{sub 2} by compensating the acceptor levels. The deep defects are likely to act as recombination centers for the photogenerated charge carriers and are thus detrimental for the performance of the photovoltaic cells. On the other hand, the formation energies of the carbon impurities are high, even under C-rich growth conditions. Thus, few C impurities will form in CuInSe{sub 2} and CuGaSe{sub 2} in thermodynamic equilibrium. However, the deposition of the precursor solution in non-vacuum growth methods presents conditions far from thermodynamic equilibrium. In this case, our calculations show that C impurities formed in non-equilibrium tend to segregate from CuInSe{sub 2} and CuGaSe{sub 2} by approaching thermodynamic equilibrium, e.g., via thorough annealing.

  15. A tem study of Y-Ba-Cu-O superconductor material prepared by plasma spraying

    SciTech Connect

    Lu, J.; Qiao, G.W.

    1988-01-01

    A transmission electron microscopy (TEM) study was made on Y-Ba-Cu-O superconductors prepared by plasma spraying which is a useful technique in forming and manufacturing of brittle materials. Amophous region and transitional phases with certain orientation relationship were found between YBa/sub 2/Cu/sub 3/O/sub 7-x/ grains.

  16. Modified Ni-Cu catalysts for ethanol steam reforming

    SciTech Connect

    Dan, M.; Mihet, M.; Almasan, V.; Borodi, G.; Katona, G.; Muresan, L.; Lazar, M. D.

    2013-11-13

    Three Ni-Cu catalysts, having different Cu content, supported on γ-alumina were synthesized by wet co-impregnation method, characterized and tested in the ethanol steam reforming (ESR) reaction. The catalysts were characterized for determination of: total surface area and porosity (N{sub 2} adsorption - desorption using BET and Dollimer Heal methods), Ni surface area (hydrogen chemisorption), crystallinity and Ni crystallites size (X-Ray Diffraction), type of catalytic active centers (Hydrogen Temperature Programmed Reduction). Total surface area and Ni crystallites size are not significantly influenced by the addition of Cu, while Ni surface area is drastically diminished by increasing of Cu concentration. Steam reforming experiments were performed at atmospheric pressure, temperature range 150-350°C, and ethanol - water molar ration of 1 at 30, using Ar as carrier gas. Ethanol conversion and hydrogen production increase by the addition of Cu. At 350°C there is a direct connection between hydrogen production and Cu concentration. Catalysts deactivation in 24h time on stream was studied by Transmission Electron Microscopy (TEM) and temperature-programmed reduction (TPR) on used catalysts. Coke deposition was observed at all studied temperatures; at 150°C amorphous carbon was evidenced, while at 350°C crystalline, filamentous carbon is formed.

  17. Modified Ni-Cu catalysts for ethanol steam reforming

    NASA Astrophysics Data System (ADS)

    Dan, M.; Mihet, M.; Almasan, V.; Borodi, G.; Katona, G.; Muresan, L.; Lazar, M. D.

    2013-11-01

    Three Ni-Cu catalysts, having different Cu content, supported on γ-alumina were synthesized by wet co-impregnation method, characterized and tested in the ethanol steam reforming (ESR) reaction. The catalysts were characterized for determination of: total surface area and porosity (N2 adsorption - desorption using BET and Dollimer Heal methods), Ni surface area (hydrogen chemisorption), crystallinity and Ni crystallites size (X-Ray Diffraction), type of catalytic active centers (Hydrogen Temperature Programmed Reduction). Total surface area and Ni crystallites size are not significantly influenced by the addition of Cu, while Ni surface area is drastically diminished by increasing of Cu concentration. Steam reforming experiments were performed at atmospheric pressure, temperature range 150-350°C, and ethanol - water molar ration of 1 at 30, using Ar as carrier gas. Ethanol conversion and hydrogen production increase by the addition of Cu. At 350°C there is a direct connection between hydrogen production and Cu concentration. Catalysts deactivation in 24h time on stream was studied by Transmission Electron Microscopy (TEM) and temperature-programmed reduction (TPR) on used catalysts. Coke deposition was observed at all studied temperatures; at 150°C amorphous carbon was evidenced, while at 350°C crystalline, filamentous carbon is formed.

  18. ESR1 mutations as a mechanism for acquired endocrine resistance in breast cancer

    PubMed Central

    Jeselsohn, Rinath; Buchwalter, Gilles; De Angelis, Carmine; Brown, Myles; Schiff, Rachel

    2016-01-01

    Most breast cancers are estrogen receptor α (ER)-positive (+) and are treated with endocrine therapies targeting ER activity. Despite efforts, the mechanisms of the frequent clinical resistance to these therapies remain largely unknown. Several recent parallel studies unveiled gain-of-function recurrent ESR1 mutations in up to 20% of patients with metastatic ER+ disease who all received endocrine therapies, which for more cases included an aromatase inhibitor. These mutations, clustered in a hotspot within the ligand-binding domain (LBD), lead to ligand independent ER activity and tumor growth, partial resistance to tamoxifen and fulvestrant, and potentially increased metastatic capacity. Together, these findings suggest that the ESR1 LBD mutations account for acquired endocrine resistance in a substantial fraction of patients with metastatic disease. The absence of detectable ESR1 mutations in treatment-naïve disease and the correlation with the number of endocrine treatments indicate a clonal expansion of rare mutant clones, selected under the pressure of treatment. New technologies to detect low/ultra rare ESR1 mutations together with tissue and liquid biopsies are required to fully expose their clinical relevance in prognosis and treatment. Pre-clinical and clinical development of rationale-based novel therapeutic strategies to inhibit these mutants has the potential to substantially improve treatment outcomes. PMID:26122181

  19. ESR spectroscopy for detecting gamma-irradiated dried vegetables and estimating absorbed doses

    NASA Astrophysics Data System (ADS)

    Kwon, Joong-Ho; Chung, Hyung-Wook; Byun, Myung-Woo

    2000-03-01

    In view of an increasing demand for food irradiation technology, the development of a reliable means of detection for the control of irradiated foods has become necessary. Various vegetable food materials (dried cabbage, carrot, chunggyungchae, garlic, onion, and green onion), which can be legally irradiated in Korea, were subjected to a detection study using ESR spectroscopy. Correlation coefficients ( R2) between absorbed doses (2.5-15 kGy) and their corresponding ESR signals were identified from ESR signals. Pre-established threshold values were successfully applied to the detection of 54 coded unknown samples of dried clean vegetables ( chunggyungchae, Brassica camestris var. chinensis), both non-irradiated and irradiated. The ESR signals of irradiated chunggyungchae decreased over a longer storage time, however, even after 6 months of ambient storage, these signals were still distinguishable from those of non-irradiated samples. The most successful estimates of absorbed dose (5 and 8 kGy) were obtained immediately after irradiation using a quadratic fit with average values of 4.85 and 8.65 kGy being calculated.

  20. Evaluating the Potential of Q-Band ESR Spectroscopy for Dose Reconstruction of Fossil Tooth Enamel.

    PubMed

    Guilarte, Verónica; Trompier, François; Duval, Mathieu

    2016-01-01

    The potential of Q-band Electron Spin Resonance (ESR) for quantitative measurements has been scarcely evaluated in the literature and its application for dose reconstruction of fossil tooth enamel with dating purposes remains still quite unknown. Hence, we have performed a comparative study based on several Early to Middle Pleistocene fossil tooth samples using both X- and Q-band spectroscopies. Our results show that Q-band offers a significant improvement in terms of sensitivity and signal resolution: it allows not only to work with reduced amounts of valuable samples (< 4 mg), but also to identify different components of the main composite ESR signal. However, inherent precision of the ESR intensity measurements at Q-band is clearly lower than that achieved at X-band, highlighting the necessity to carry out repeated measurements. All dose values derived from X- and Q-band are nevertheless systematically consistent at either 1 or 2 sigma. In summary, our results indicate that Q-band could now be considered as a reliable tool for ESR dosimetry/dating of fossil teeth although further work is required to improve the repeatability of the measurements. PMID:26930398

  1. ESR dating of tooth enamel from yunxian homo erectus site, China

    NASA Astrophysics Data System (ADS)

    Chen, Tie-Mei; Yang, Quan; Hu, Yan-Qiu; Bao, Wen-Bo; Li, Tian-Yuan

    Two almost complete fossil hominid crania (EV9001 and EV9002) were found in 1989 and 1990 in Middle Pleistocene terrace deposit of Han River, Yunxian county, Hubei province, China. They are classified as Homo erectus. Nine fossil animal teeth stratigraphically associated with the skulls were selected for electron spin resonance (ESR) dating. The simple exponential function was used for determination of the accumulated dose De and its appropriateness was discussed on the base of the experimental study. The closed system assumption was checked and the early uranium uptake model was applied to age determination. A mean age value was yielded to be 581±93 ka. It deviates from the palaeomagnetic dating result of 830-870 ka. Micro-regional complete saturation of ESR signal in enamel of very high U-content may account for the underestimation of ESR ages. Nevertheless both ESR and palaeomagnetic dating results place Yunxian crania in between the Homo erectus of Lantian and Zhoukoudian, which means that Yunxian crania constitute an important link in the human evolutionary lineage of China.

  2. Evaluating the Potential of Q-Band ESR Spectroscopy for Dose Reconstruction of Fossil Tooth Enamel

    PubMed Central

    Guilarte, Verónica; Trompier, François; Duval, Mathieu

    2016-01-01

    The potential of Q-band Electron Spin Resonance (ESR) for quantitative measurements has been scarcely evaluated in the literature and its application for dose reconstruction of fossil tooth enamel with dating purposes remains still quite unknown. Hence, we have performed a comparative study based on several Early to Middle Pleistocene fossil tooth samples using both X- and Q-band spectroscopies. Our results show that Q-band offers a significant improvement in terms of sensitivity and signal resolution: it allows not only to work with reduced amounts of valuable samples (< 4 mg), but also to identify different components of the main composite ESR signal. However, inherent precision of the ESR intensity measurements at Q-band is clearly lower than that achieved at X-band, highlighting the necessity to carry out repeated measurements. All dose values derived from X- and Q-band are nevertheless systematically consistent at either 1 or 2 sigma. In summary, our results indicate that Q-band could now be considered as a reliable tool for ESR dosimetry/dating of fossil teeth although further work is required to improve the repeatability of the measurements. PMID:26930398

  3. Quantum chemical study of ZnO, Cu/ZnO, Cu/sub 2/O, and CuO clusters and CO chemisorption on ZnO(0001), CuZnO(0001), and Cu/ZnO(0001) surfaces

    SciTech Connect

    Rodriguez, J.A.; Campbell, C.T.

    1987-12-31

    Copper/zinc oxide mixtures show strong synergistic effects when used together as catalysts, particularly in methanol synthesis and water-gas-shift reactions. The authors have employed semiempirical quantum-mechanical calculations (INDO) to study the electronic properties of ZnO, CuO, and CuO/sub 2/ clusters (less than or equal to 26 atoms), of Cu absorbed on or substituted in these ZnO clusters, and of CO chemisorbed on ZnO(0001) and Cu/ZnO clusters. The results are discussed in light of models previously proposed to explain the unique properties of Cu/ZnO catalysts, which often involve Cu/sup +/ impurities in (on) the ZnO lattice. They use mainly the calculated charge on the Cu atom and its interaction with CO to address the electronic properties of Cu substituted in and adsorbed on ZnO clusters. Their results for neutral clusters indicate that, with respect to atomic charge, this Cu is quite similar in nature to the Cu atoms of bulk CuO or the Zn atoms of ZnO, where the metal has a formal oxidation state of +2. The Cu site in these ZnO clusters shows unique electron affinity properties, accepting a major fraction of the added electron density for anionic clusters. The mechanisms of CO chemisorptive bond formation on Cu(100), ZnO(0001), and Cu-doped ZnO are compared and contrasted based on the present results and those in the literature.

  4. Structural and optical studies on antimony and zinc doped CuInS2 thin films

    NASA Astrophysics Data System (ADS)

    Ben Rabeh, M.; Chaglabou, N.; Kanzari, M.; Rezig, B.

    2009-11-01

    The influence of Zn and Sb impurities on the structural, optical and electrical properties of CuInS2 thin films on corning 7059 glass substrates was studied. Undoped and Zn or Sb doped CuInS2 thin films were deposited by thermal evaporation method and annealed in vacuum at temperature of 450 ∘C Undoped thin films were grown from CuInS2 powder using resistively heated tungsten boats. Zn species was evaporated from a thermal evaporator all together to the CuInS2 powder and Sb species was mixed in the starting powders. The amount of the Zn or Sb source was determined to be in the range 0-4 wt% molecular weight compared with the CuInS2 alloy source. The films were studied by means of X-ray diffraction (XRD), Optical reflection and transmission and resistance measurements. The films thicknesses were in the range 450-750 nm. All the Zn: CuInS2 and Sb: CuInS2 thin films have relatively high absorption coefficient between 104 cm-1 and 105 cm-1 in the visible and the near-IR spectral range. The bandgap energies are in the range of 1.472-1.589 eV for Zn: CuInS2 samples and 1.396-1.510 eV for the Sb: CuInS2 ones. The type of conductivity of these films was determined by the hot probe method. Furthermore, we found that Zn and Sb-doped CuInS2 thin films exhibit P type conductivity and we predict these species can be considered as suitable candidates for use as acceptor dopants to fabricate CuInS2-based solar cells.

  5. Experimental and computational simulation studies on creep deformation mechanisms of a novel nanostructured Cu and Cu-10%Sn Alloy

    NASA Astrophysics Data System (ADS)

    Abo-Elsoud, Mohamed A.

    2015-04-01

    This work presents experimental and computational simulation studies on creep deformation mechanisms of a novel nanostructured Cu and Cu-10%Sn alloy that prepared by mechanical alloying (MA) copper with elemental Tin. Mechanical Newtonian creep model is employed for computational simulation of creep deformation mechanism under low stress-high temperature and to justify the experimental findings. The observed behaviors are discussed and compared with the predications of the Nabarro-Herring (N-H) theory of directional diffusion. A simple theory based on the climb controlled generation of dislocations from a fixed density of sources is developed to explain the observed behavior. TEM and SEM investigations are convenient and powerful techniques for characterization of phases and a novel nano-grain structured of the resulting materials. The reduction of grain size to the nanometer scale improves their mechanical properties.

  6. The Comparison of The Effects of Silybin and Silybin-Phosphatidylcholine on Viability and ESR Expression in Human Breast Cancer T47D Cell Line

    PubMed Central

    Mahmoodi, Narges; Motamed, Nasrin; Paylakhi, Seyed Hassan

    2014-01-01

    Objective Silybin is a polyphenol with anti-oxidant and anti-cancer properties. The poor bioavailability of some polyphenols can be improved by binding to phosphatidylcholine. In recent years, studies have been conducted to evaluate the anti-cancer effect of silybin. We studied the effect of silybin and silybin-phosphatidylcholine on ESR1 and ESR2 gene expression and viability in the T47D breast cancer cell line. Materials and Methods In this experimental study, a 3-(4,5-Dimethylthiazol-2-Yl)-2,5-Diphenyltetrazolium Bromide test (MTT test) was used to determine doses for cell treatment, and the gene expression was analyzed by real-time reverse transcriptase-polymerase chain reaction (real-time RT- PCR). Results Significant dose- and time-dependent cell growth inhibitory effects of silybin and silybin-phosphatidylcholine along with ESR1 down-regulation were observed in T47D cells. In contrast to ESR1, the T47D cell line showed negligible ESR2 expression. Conclusion This study suggests that silybin and silybin-phosphatidylcholine down-regulate ESR1 in ER+breast cancers. Results also show that in the T47D cell line, silybindown-regulation of ESR1 compared with silybin. PMID:24611152

  7. Ionosphere and Thermosphere above EISCAT-ESR during IPY

    NASA Astrophysics Data System (ADS)

    Blelly, Pierre-Louis; Alcaydé, Denis; van Eyken, Antony P.

    2010-05-01

    In a previous study we showed that, with the use of 13-moment, parallel, two-ion (atomic and molecular) energy equations to fit the full Incoherent Scatter (IS) profiles along the magnetic field, it was possible to overcome two major difficulties for a proper analysis of the ion energy budget in the F1- and F2-regions, namely getting accurate estimates of the ion composition in the F1-region, and then being able to separate the relative contributions from the neutral atmosphere and from frictional heating. It was shown that this "full profile" method is sufficiently robust for routine use, even for periods with moderately high convection electric fields. In the present study, the method is applied to the three-year IS dataset recorded at the EISCAT Svalbard Radar (ESR) during the International Polar Year (IPY ) period (March. 2007 - Sept. 2009), and the results are used to study long-term variations in the ionosphere and neutral atmosphere. For that purpose, we choose to use a similar approach to that used in the MSIS models for determining the time variability of the measured/inferred parameters and built what we call ESR-IPY models of ionospheric and atmospheric parameters. After discussing a case-day example for which the quality of the global models fits is shown, the long term behavior (year-to-year, seasonal, solar flux and geomagnetic activity) is shown and contrasted, when available, with existing standard models such as MSIS and IRI. Key words. Polar cap ionosphere, Ionosphere/atmosphere interactions, Modelling and forecasting

  8. Characterization of structure and thermophysical properties of three ESR slags

    NASA Astrophysics Data System (ADS)

    Plotkowski, A.; deBarbadillo, J.; Krane, Matthew J. M.

    2016-07-01

    The structure and properties of electroslag remelting (ESR) slags were characterized. Slags samples of three compositions were obtained from industrial remelting processes at Special Metals Corporation and from casting in a laboratory vacuum induction melter. The structure of the slag samples was observed using optical and electron microscopy, and phases were identified and their relative amounts quantified using X-ray diffraction. Laser flash thermal diffusivity, density, and differential scanning calorimetry measurements for specific heat were performed to determine the bulk thermal conductivity of the samples. Sample porosity was measured as a function of depth using a serial sectioning technique, and a onedimensional computational model was developed to estimate the thermal conductivity of the fully dense slags. These results are discussed in context with previous studies, and opportunities for future research are identified. AFRL Case Number: 88ABW-2015-1871.

  9. Strong resistance of Arabidopsis thaliana and Raphanus sativus seeds for ionizing radiation as studied by ESR, ENDOR, ESE spectroscopy and germination measurement: Effect of long-lived and super-long-lived radicals

    NASA Astrophysics Data System (ADS)

    Kumagai, Jun; Katoh, Hiromi; Kumada, Takayuki; Tanaka, Atsushi; Tano, Shigemitsu; Miyazaki, Tetsuo

    2000-01-01

    Resistance of seeds for ionizing radiation effects on Arabidopsis thaliana and Raphanus sativus seeds were investigated by ESR, ENDOR, ESE spectroscopy and germination measurement. Two types of free radicals, such as long-lived (LL) and super-long-lived (SL) radicals, were produced by the γ-irradiation in the seeds. More than 90% of the 1 kGy-irradiated-seeds can germinate probably by decreasing the LL radicals by absorbing water. 10 kGy-irradiated-seeds cannot germinate at all probably due to the existence of significant amounts of the SL radicals even after absorbing water.

  10. ESR dating of submarine hydrothermal activities using barite in sulfide deposition

    NASA Astrophysics Data System (ADS)

    Toyoda, S.; Fujiwara, T.; Ishibashi, J.; Isono, Y.; Uchida, A.; Takamasa, A.; Nakai, S.

    2012-12-01

    The temporal change of submarine hydrothermal activities has been an important issue in the aspect of the evolution of hydrothermal systems which is related with ore formation (Urabe, 1995) and biological systems sustained by the chemical species arising from hydrothermal activities (Macdonald et al., 1980). Determining the ages of the hydrothermal deposit will provide essential information on such studies. Dating methods using disequilibrium between radioisotopes such as U-Th method (e.g. You and Bickle, 1998), 226}Ra-{210Pb and 228}Ra-{228Th method (e.g. Noguchi et al., 2011) have been applied to date submarine hydrothermal deposits. ESR (electron spin resonance) dating method is commonly applied to fossil teeth, shells, and quartz of Quaternay period where the natural accumulated dose is obtained from the intensities of the ESR signals which are created by natural radiation. The natural dose is divided by the dose rate to the mineral/sample to deduce the age. Okumura et al., (2010) made the first practical application of ESR (electron spin resonance) dating technique to a sample of submarine hydrothermal barite (BaSO4) to obtain preliminary ages, where Kasuya et al. (1991) first pointed out that barite can be used for ESR dating. Knowing that ESR dating of barite is promising, in this paper, we will present how we have investigated each factor that contributes ESR dating of barite in submarine hydrothermal sulfide deposition. (1) The best ESR condition for measuring the SO3- signal in barite is with the microwave power of 1mW and modulation amplitude of 0.1mT. (2) As results of heating experiments, the signal was found to be stable for the dating age range of several thousands. (3) 226Ra replacing Ba in barite is the source of the radiation. The amount of radioactive elements in sulfide mineral surrounding barite is negligible. (4) The external radiation from the sea water is negligible even in the submarine hydrothermal area where the radiation level is much

  11. First-principles study of carbon impurities in CuInSe2 and CuGaSe2, present in non-vacuum synthesis methods

    NASA Astrophysics Data System (ADS)

    Bekaert, J.; Saniz, R.; Partoens, B.; Lamoen, D.

    2015-01-01

    A first-principles study of the structural and electronic properties of carbon impurities in CuInSe2 and CuGaSe2 is presented. Carbon is present in organic molecules in the precursor solutions used in non-vacuum growth methods for CuInSe2 and CuGaSe2 based photovoltaic cells. These growth methods make more efficient use of material, time, and energy than traditional vacuum methods. The formation energies of several carbon impurities are calculated using the hybrid HSE06 functional. CCu acts as a shallow donor, CIn and interstitial C yield deep donor levels in CuInSe2, while in CuGaSe2 CGa and interstitial C act as deep amphoteric defects. So, these defects reduce the majority carrier (hole) concentration in p-type CuInSe2 and CuGaSe2 by compensating the acceptor levels. The deep defects are likely to act as recombination centers for the photogenerated charge carriers and are thus detrimental for the performance of the photovoltaic cells. On the other hand, the formation energies of the carbon impurities are high, even under C-rich growth conditions. Thus, few C impurities will form in CuInSe2 and CuGaSe2 in thermodynamic equilibrium. However, the deposition of the precursor solution in non-vacuum growth methods presents conditions far from thermodynamic equilibrium. In this case, our calculations show that C impurities formed in non-equilibrium tend to segregate from CuInSe2 and CuGaSe2 by approaching thermodynamic equilibrium, e.g., via thorough annealing.

  12. A study of ternary Cu2SnS3 and Cu3SnS4 thin films prepared by sulfurizing stacked metal precursors

    NASA Astrophysics Data System (ADS)

    Fernandes, P. A.; Salomé, P. M. P.; da Cunha, A. F.

    2010-06-01

    Thin films of Cu2SnS3 and Cu3SnS4 were grown by sulfurization of dc magnetron sputtered Sn-Cu metallic precursors in a S2 atmosphere. Different maximum sulfurization temperatures were tested which allowed the study of the Cu2SnS3 phase changes. For a temperature of 350 °C the films were composed of tetragonal (I-42m) Cu2SnS3. The films sulfurized at a maximum temperature of 400 °C presented a cubic (F-43m) Cu2SnS3 phase. On increasing the temperature up to 520 °C, the Sn content of the layer decreased and orthorhombic (Pmn21) Cu3SnS4 was formed. The phase identification and structural analysis were performed using x-ray diffraction (XRD) and electron backscattered diffraction (EBSD) analysis. Raman scattering analysis was also performed and a comparison with XRD and EBSD data allowed the assignment of peaks at 336 and 351 cm-1 for tetragonal Cu2SnS3, 303 and 355 cm-1 for cubic Cu2SnS3, and 318, 348 and 295 cm-1 for the Cu3SnS4 phase. Compositional analysis was done using energy dispersive spectroscopy and induced coupled plasma analysis. Scanning electron microscopy was used to study the morphology of the layers. Transmittance and reflectance measurements permitted the estimation of absorbance and band gap. These ternary compounds present a high absorbance value close to 104 cm-1. The estimated band gap energy was 1.35 eV for tetragonal (I-42m) Cu2SnS3, 0.96 eV for cubic (F-43m) Cu2SnS3 and 1.60 eV for orthorhombic (Pmn21) Cu3SnS4. A hot point probe was used for the determination of semiconductor conductivity type. The results show that all the samples are p-type semiconductors. A four-point probe was used to obtain the resistivity of these samples. The resistivities for tetragonal Cu2SnS3, cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4 are 4.59 × 10-2 Ω cm, 1.26 × 10-2 Ω cm, 7.40 × 10-4 Ω cm, respectively.

  13. Structural properties of CuO4 and CuO5 clusters: A density functional study

    NASA Astrophysics Data System (ADS)

    Massobrio, Carlo; Pouillon, Yann

    2003-10-01

    We determine the equilibrium structures of CuO4 and CuO5 clusters within the framework of density functional theory and a plane-wave approach. Our calculations go beyond qualitative structural assignments proposed to interpret photoelectron spectroscopy measurements. We found that the lowest energy structures for CuO4 are based on Cu(O2) units, isomers containing Cu(O3) ozonide units being higher in energy. A different situation is observed in the case of CuO5, where several isomers with one O3 motif lie at lower energy than those made of Cu(O2) units only. Ozonide units appear crucial to ensure the stability of CuO5 clusters. This is achieved by a larger hybridization between Cu3d-like and O2p-like states, which persists when the ozonide unit transforms into an O3 chain.

  14. Comparative study of the alloying effect on the initial oxidation of Cu-Au(100) and Cu-Pt(100)

    SciTech Connect

    Luo, Langli; Zhou, Guangwen; Kang, Yihong; Yang, Judith C.; Su, Dong; Stach, Eric A.

    2014-03-24

    Using in situ transmission electron microscopy, we show that the oxidation of the Cu-Au(100) results in the formation of Cu{sub 2}O islands that deeply embed into the Cu-Au substrate while the oxidation of the Cu-Pt(100) leads to the formation of Cu{sub 2}O islands that highly protrude above the Cu-Pt substrate. Their difference is attributed to the different mobilities of Pt and Au in the Cu base alloys for which the sluggish mobility of Pt in Cu results in trapped Pt atoms at the oxide/alloy interface while the faster mobility of Au in Cu leads to enhanced rehomogenization of the alloy composition.

  15. Lack of Association between ESR1 and CYP1A1 Gene Polymorphisms and Susceptibility to Uterine Leiomyoma in Female Patients of Iranian Descent

    PubMed Central

    Taghizade Mortezaee, Fatemeh; Tabatabaiefar, Mohammad Amin; Hashemzadeh Chaleshtori, Morteza; Miraj, Sepideh

    2014-01-01

    Uterine leiomyoma (UL) is the most common benign smooth muscle cell tumor with as yet unknown etiology and pathogenesis. This study was carried out to investigate the association of ESR1-351 A>G, ESR1 -397 T>C and CYP1A1 (Ile462Val) polymorphisms with UL in female patients of Iranian origin. In this case-control study, 276 patients with UL and 156 healthy women were recruited. The genetic polymorphisms ESR1-351 A>G, ESR1-397 T>C and CYP1A1 (Ile462Val) were genotyped by polymerase chain reaction- restriction fragment length polymorphism (PCR-RFLP). No significant difference were found in frequencies of both genotypes and alleles of ESR1-351 A>G, ESR1-397 T>C and CYP1A1 (Ile462Val) polymorphisms between the two groups (p>0.05). Our findings indicated that these ESR1 and CYP1A1 polymorphisms were not associated with the development of UL in the cases reported here. PMID:24567938

  16. ESR measurement of radical clearance in lung of whole mouse

    SciTech Connect

    Takeshita, K.; Utsumi, H.; Hamada, A. )

    1991-06-14

    Clearance of the nitroxide radicals, hydroxy-TEMPO and carboxy-PROxYL, in whole-mouse lung was directly measured by in vivo ESR. After injecting a nitroxide radical, distribution of the nitroxide radical all over the lung was confirmed by ESR imaging. The ESR signal of hydroxy-TEMPO was reduced in the lung and the clearance obeyed first-order kinetics, whereas the signal of carboxy-PROxYL remained constant. Comparison of the clearance rates of live and dead mice indicated the presence of 2 different clearance systems in the lung: loss of its paramagnetism in the lung, and transfer from alveolar to the blood circulation system.

  17. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using x-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  18. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  19. Association between estrogen receptor alpha (ESR1) gene polymorphisms and severe preeclampsia.

    PubMed

    Molvarec, Attila; Vér, Agota; Fekete, Andrea; Rosta, Klára; Derzbach, László; Derzsy, Zoltán; Karádi, István; Rigó, János

    2007-03-01

    Associations have been reported between estrogen receptor alpha (ESR1) gene polymorphisms and various pathological conditions, including cardiovascular diseases. Our aim was to investigate whether two polymorphisms of the ESR1 gene (ESR1 c.454 -397T>C: PvuII restriction site and c.454 -351A>G: XbaI restriction site) are associated with preeclampsia. In a case-control study, we analyzed blood samples from 119 severely preeclamptic patients and 103 normotensive, healthy pregnant women using the polymerase chain reaction (PCR)-restriction fragment length polymorphism (RFLP) method. All of the women were Caucasian. There was no association between severe preeclampsia and the PvuII and XbaI ESR1 gene polymorphisms separately. However, with the simultaneous carriage of both polymorphisms, the TT/AA genotype combination was significantly more frequent in severely preeclamptic patients than in healthy control subjects (24.4% vs. 9.7%, p=0.003), whereas the TT/AG combination was significantly less frequent in the severely preeclamptic group than in the control group (5.0% vs. 18.4%, p=0.002). According to the haplotype estimation, the homozygous T-A haplotype carriers had an increased risk of severe preeclampsia independent of maternal age, prepregnancy BMI, primiparity and smoking status (adjusted odds ratio [OR]: 4.36, 95% confidence interval [CI]: 1.65-11.53). The GG genotype of the XbaI polymorphism was associated with a lower risk of fetal growth restriction in patients with severe preeclampsia (OR: 0.23, 95% CI: 0.07-0.73). In conclusion, the homozygous T-A haplotype carriers of ESR1 PvuII and XbaI polymorphisms showed an increased risk of severe preeclampsia. In addition, the GG genotype of the XbaI polymorphism decreased the risk of fetal growth restriction in severely preeclamptic patients. PMID:17510501

  20. Preferential Cu precipitation at extended defects in bcc Fe: An atomistic study

    SciTech Connect

    Zhang, Yongfeng; Millett, Paul C.; Tonks, Michael R.; Bai, Xian-Ming; Biner, S. Bulent

    2015-04-01

    As a starting point to understand Cu precipitation in RPV alloys, molecular dynamics and Metropolis Monte-Carlo simulations are carried out to study the effect of lattice defects on Cu precipitation by taking Fe-Cu system as a model alloy. Molecular dynamics simulations show that owing to the high heat of mixing and positive size mismatch, Cu is attracted by vacancy type defects such as vacancies and voids, and tensile stress fields. In accordance, preferential precipitation of Cu is observed in Metropolis Monte-Carlo simulations at dislocations, prismatic loops and voids. The interaction of Cu with a stress field, e.g., that associated with a dislocation or a prismatic loop, is dominated by elastic effect and can be well described by the linear-elasticity theory. For prismatic loops, the attraction to Cu is found to be size-dependent with opposite trends displayed by vacancy and interstitial loops. The size-dependences can be explained by considering the stress fields produced by these loops. The current results will be useful for understanding the effect of neutron irradiation on Cu precipitation in reactor-pressure-vessel steels.

  1. Ab-initio study of donor-acceptor codoping for n-type CuO

    SciTech Connect

    Peng, Yuan; Wang, Junling; Zheng, Jianwei; Wu, Ping

    2014-10-28

    Single n-type dopant in CuO has either a deep donor level or limited solubility, inefficient in generating free electrons. We have performed ab-initio study of the donor-acceptor codoping to obtain n-type CuO. Our results show that N codoping can slightly improve the donor level of Zr and In by forming shallower n-type complexes (Zr{sub Cu}-N{sub O} and 2In{sub Cu}-N{sub O}), but their formation energies are too high to be realized in experiments. However, Li codoping with Al and Ga is found to be relatively easy to achieve. 2Al{sub Cu}-Li{sub Cu} and 2Ga{sub Cu}-Li{sub Cu} have shallower donor levels than single Al and Ga by 0.14 eV and 0.08 eV, respectively, and their formation energies are reasonably low to act as efficient codopants. Moreover, Li codoping with both Al and Ga produce an empty impurity band just below the host conduction band minimum, which may reduce the donor ionization energy at high codoping concentrations.

  2. First-Principles Study of CuGaO2 Polymorphs: Delafossite α-CuGaO2 and Wurtzite β-CuGaO2.

    PubMed

    Suzuki, Issei; Nagatani, Hiraku; Kita, Masao; Iguchi, Yuki; Sato, Chiyuki; Yanagi, Hiroshi; Ohashi, Naoki; Omata, Takahisa

    2016-08-01

    The electronic structures of delafossite α-CuGaO2 and wurtzite β-CuGaO2 were calculated based on density functional theory using the local density approximation functional including the Hubbard correction (LDA+U). The differences in the electronic structure and physical properties between the two polymorphs were investigated in terms of their crystal structures. Three major structural features were found to influence the electronic structure. The first feature is the atomic arrangements of cations. In the conduction band of α-CuGaO2 with a layered structure of Cu2O and Ga2O3, Cu and Ga states do not mix well; the lower part of the conduction band mainly consists of Cu 4s and 4p states, and the upper part consists of Ga 4s and 4p states. By contrast, in β-CuGaO2, which is composed of CuO4 and GaO4 tetrahedra, Cu and Ga states are well-mixed. The second feature is the coordination environment of Cu atoms; the breaking of degeneracy of Cu 3d orbitals is determined by the crystal field. Dispersion of the Cu 3d valence band of β-CuGaO2, in which Cu atoms are tetrahedrally coordinated to oxygen atoms, is smaller than those in α-CuGaO2, in which Cu atoms are linearly coordinated to oxygen atoms; this results in a larger absorption coefficient and larger hole effective mass in β-CuGaO2 than in α-CuGaO2. The interatomic distance between Cu atoms-the third feature-also influences the dispersion of the Cu 3d valence band (i.e., the effective hole mass); the effective hole mass decreases with decreasing interatomic distance between Cu atoms in each structure. The results obtained are valuable for understanding the physical properties of oxide semiconductors containing monovalent copper and silver. PMID:27438905

  3. Spectroscopic studies of interaction between CuO nanoparticles and bovine serum albumin.

    PubMed

    Esfandfar, Paniz; Falahati, Mojtaba; Saboury, AliAkbar

    2016-09-01

    Recently, the great interests in manufacturing and application of metal oxide nanoparticles in commercial and industrial products have led to focus on the potential impact of these particles on biomacromolecules. In the present study, the interaction of copper oxide (CuO) nanoparticles with bovine serum albumin (BSA) was studied by spectroscopic techniques. The zeta potential value for BSA and CuO nanoparticles with average diameter of around 50 nm at concentration of 10 μM in the deionized (DI) water were -5.8 and -22.5 mV, respectively. Circular dichroism studies did not show any changes in the content of secondary structure of the protein after CuO nanoparticles interaction. Fluorescence data revealed that the fluorescence quenching of BSA by CuO nanoparticles was the result of the formed complex of CuO nanoparticles - BSA. Binding constants and other thermodynamic parameters were determined at three different temperatures. The hydrogen bond interactions are the predominant intermolecular forces to stabilize the CuO nanoparticle - BSA complex. This study provides important insight into the interaction of CuO nanoparticles with proteins, which may be of importance for further application of these nanoparticles in biomedical applications. PMID:26555383

  4. Synthesis, spectral, thermal and theoretical studies of Cu(II) complexes with 3-[4‧-dimethylaminophenyl]-1-(2-pyridyl)prop-2-en-1-one (DMAPP)

    NASA Astrophysics Data System (ADS)

    Gaber, M.; El-Daly, S. A.; El-Sayed, Y. S. Y.

    2009-03-01

    Cu(II) complexes of 3-[4'-dimethylaminophenyl]-1-(2-pyridyl) prop-2-en-1-one (DMAPP) are prepared and characterized by elemental analysis as well as spectral studies (IR and UV-vis), ESR, magnetic susceptibilities and thermal studies. The effect of different alcoholic solvents as well as the temperature on the complex formation is studied. The effect of Cu(II) ion on the emission spectrum of the free chalcone is also assigned. The stoichiometry, stability constant, absorption maximum and molar absorptivity of the metal complexes as well as the effect of pH, temperature on complex formation are determined spectrophotometrically. Adherence to Beer's law and Ringbom optimum concentration ranges are determined. The thermal decomposition of the metal complexes is studied by TGA technique. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation are estimated. The structure of complexes was energetically optimized through molecular mechanics applying MM + force field coupled with molecular dynamics simulation.

  5. Synthesis, spectroscopic, antimicrobial and DNA cleavage studies of new Co(II), Ni(II), Cu(II), Cd(II), Zn(II) and Hg(II) complexes with naphthofuran-2-carbohydrazide Schiff base

    NASA Astrophysics Data System (ADS)

    Halli, Madappa B.; Sumathi, R. B.

    2012-08-01

    A series of Co(II), Ni(II), Cu(II), Cd(II), Zn(II) and Hg(II) complexes have been synthesized with newly synthesized Schiff base derived from naphthofuran-2-carbohydrazide and cinnamaldehyde. The elemental analyses of the complexes are confined to the stoichiometry of the type MLCl2 [M = Co(II) and Cu(II)], ML2Cl2 [M = Ni(II), Cd(II), Zn(II) and Hg(II)] respectively, where L is Schiff base ligand. Structures have been proposed from elemental analyses, IR, electronic, mass, 1H NMR, ESR spectral data, magnetic, and thermal studies. The measured low molar conductance values in DMF indicate that the complexes are non-electrolytes. Spectroscopic studies suggest coordination occurs through azomethine nitrogen and carbonyl oxygen of the ligand with the metal ions. The Schiff base and its complexes have been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Salmonella typhi) and antifungal (Aspergillus niger, Aspergillus flavus, Cladosporium and Candida albicans) activities by minimum inhibitory concentration (MIC) method. The DNA cleavage studies by agarose gel electrophoresis method was studied for all the complexes.

  6. Giant magnetoresistance studies in evaporated Ni-Fe/Cu and Ni-Fe-Co/Cu multilayers (abstract)

    NASA Astrophysics Data System (ADS)

    Haftek, E.; Zeltser, A. M.; Smith, Neil

    1997-04-01

    Room temperature giant magnetoresistance (GMR) and magnetic properties of (Ni-Fe/Cu)n and (Ni-Fe-Co/Cu)n multilayers were investigated. Alternating layers of Ni-Fe-(Co) and Cu were electron-beam evaporated in a computer-controlled high-vacuum system at base pressure of ⩽4×10-8 Torr and deposition rates of ⩽2 Å/s. To complement and expand our previous investigation,1 GMR properties were additionally studied here as a function of cobalt content of Ni-Fe-Co films, the number (n) of bilayers, deposition temperature, and type of buffer layer. The Co content was varied from 7 to 17 at. %, and the number of bilayers ranged from n=8 to 20. No significant GMR was observed in the as-deposited multilayers. To produce tangible GMR, these multilayers were annealed between 300 and 360 °C for 2 h in a 150 Oe magnetic field in an argon atmosphere. The GMR effect (ΔR/R) was essentially independent of copper spacer thickness, which varied between 25 and 30 Å. For Co containing multilayers the highest ΔR/R=7.6% was obtained for 17 at. % Co deposited at 100 °C. The ΔR/R in all Ni-Fe-Co/Cu multilayers was sensitive to the deposition temperature, and R-H loops always showed significant hysteresis independent of the type of buffer layer. For application of these materials to very high density reproduce heads,2 the best results were obtained for (27 Å NiFe/25 Å Cu)14-18 multilayers deposited at 160 °C on 70 Å Ta buffer layer. For example, n=17 multilayers annealed at 350 °C exhibited ΔR/R=7.5%, half-width at half-maximum of ˜50 Oe, essentially no anisotropy, and virtually zero hysteresis (Fig. 1). Frequency dependent permeability measurements showed constant permeability between 10 and 200 MHz. Low- and high-angle x-ray diffraction as well as atomic force microscopy were used to investigate the effect of different geometries of multilayers on structure and roughness and to correlate them with GMR properties.

  7. Growth and microtopographic study of CuInSe2 single crystals

    NASA Astrophysics Data System (ADS)

    Chauhan, Sanjaysinh M.; Chaki, Sunil; Tailor, J. P.; Deshpande, M. P.

    2016-05-01

    The CuInSe2 single crystals were grown by chemical vapour transport (CVT) technique using iodine as transporting agent. The elemental composition of the as-grown CuInSe2 single crystals was determined by energy dispersive analysis of X-ray (EDAX). The unit cell crystal structure and lattice parameters were determined by X-ray diffraction (XRD) technique. The surface microtopographic study of the as-grown CuInSe2 single crystals surfaces were done to study the defects, growth mechanism, etc. of the CVT grown crystals.

  8. New data on Cu-exchanged phillipsite: a multi-methodological study

    NASA Astrophysics Data System (ADS)

    Gatta, G. Diego; Cappelletti, Piergiulio; de'Gennaro, Bruno; Rotiroti, Nicola; Langella, Alessio

    2015-10-01

    The cation exchange capacity of a natural phillipsite-rich sample from the Neapolitan Yellow Tuff, Southern Italy (treated in order to obtain a 95 wt% zeolite-rich sample composed mainly of phillipsite and minor chabazite) for Cu was evaluated using the batch exchange method. The sample had previously been exchanged into its monocationic form (Na), and then used for the equilibrium studies of the exchange reaction 2Na+ ⇆ Cu2+. Reversibility ion exchange tests were performed. The isotherm displays an evident hysteresis loop. Interestingly, the final Cu-exchanged polycrystalline material was green-bluish. Natural, Na- and Cu-exchanged forms were analyzed by X-ray powder diffraction, and the Cu-phillipsite was also investigated by transmission electron microscopy (TEM). Structure refinement of Cu-phillipsite was performed by the Rietveld method using synchrotron data, and it indicates a small, but significant, fraction of Cu sharing with Na two-three independent extra-framework sites. The TEM experiment shows sub-spherical nano-clusters of crystalline species (with average size of 5 nm) lying on the surfaces of zeolite crystals or dispersed in the amorphous fraction, with electron diffraction patterns corresponding to those of CuO (tenorite-like structure) and Cu(OH)2 (spertiniite-like structure). X-ray and TEM investigations show that Cu is mainly concentrated in different species (crystalline or amorphous) within the sample, not only in phillipsite. The experimental findings based on X-ray and TEM investigations, along with the hysteresis loop of the ion exchange tests, are discussed and some general considerations about the mechanisms of exchange reactions involving divalent cations with high hydration energy are provided.

  9. The use of ESR spectroscopy for the identification and dose assessment of irradiated pink shrimp (Parapenaeus longirostris) from Turkey

    NASA Astrophysics Data System (ADS)

    Aydaş, Canan; Tepe Çam, Semra; Engin, Birol; Aydın, Talat; Polat, Mustafa

    2013-03-01

    Turkish pink shrimp (Parapenaeus longirostris) samples were studied by electron spin resonance (ESR) spectroscopy for identification and dose assessment purposes. In this work, the calcified shells of shrimps were used as a sample material. Before irradiation, all shrimp shell samples exhibit one weak ESR singlet with a g-factor of 2.0047. After irradiation, all samples exhibit two asymmetric ESR signal components centered at g-values of 2.0013 and 1.9959. The dose-response curves of the samples exposed to gamma radiations were found to be described well by a single saturation exponential function. Variation of ESR signal intensity of irradiated samples at room and-20 °C temperatures with time in a long-term showed that free radicals responsible from the ESR spectrum of shrimp shells were not stable but still detectable after 87 days. Also, the kinetic behavior of signal at g=2.0013 was studied and the additive dose method was used to evaluate the dose in the product.

  10. A novel analytical method to evaluate directly catalase activity of microorganisms and mammalian cells by ESR oximetry.

    PubMed

    Nakamura, Keisuke; Kanno, Taro; Mokudai, Takayuki; Iwasawa, Atsuo; Niwano, Yoshimi; Kohno, Masahiro

    2010-09-01

    Electron spin resonance (ESR) oximetry technique was applied for analysis of catalase activity in the present study. Catalase activity was evaluated by measuring oxygen from the reaction between hydrogen peroxide (H(2)O(2)) and catalase-positive cells. It was demonstrated that the ESR spectra of spin-label probes, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPOL), 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy (4-oxo-TEMPO) and 4-maleimido-2,2,6,6-tetramethyl-1-piperidinyloxy (4-maleimido-TEMPO) in the presence of H(2)O(2) were broadened with the concentrations of catalase. It was possible to make a calibration curve for catalase activity by peak widths of the spectra of each spin-label probe, which are broadened dependently on catalase concentrations. The broadened ESR spectra were also observed when the catalase-positive micro-organisms or the mammalian cells originally from circulating monocytes/macrophages were mixed with TEMPOL and H(2)O(2). Meanwhile, catalase-negative micro-organisms caused no broadening change of ESR spectra. The present study indicates that it is possible to evaluate directly the catalase activity of various micro-organisms and mammalian cells by using an ESR oximetry technique. PMID:20815766

  11. Multifrequency EPR studies of [Cu(1.5)Cu(1.5)](+) for Cu2(mu-NR2)2 and Cu2(mu-PR2)2 diamond cores.

    PubMed

    Mankad, Neal P; Harkins, Seth B; Antholine, William E; Peters, Jonas C

    2009-08-01

    Multifrequency electron paramagnetic resonance (EPR) spectroscopy is used to explore the electronic structures of a series of dicopper complexes of the type {(LXL)Cu}(2)(+). These complexes contain two four-coordinate copper centers of highly distorted tetrahedral geometries linked by two [LXL](-) ligands featuring bridging amido or phosphido ligands and associated thioether or phosphine chelate donors. Specific chelating [LXL](-) ligands examined in this study include bis(2-tert-butylsulfanylphenyl)amide (SNS), bis(2-di-iso-butylphosphinophenyl)amide (PNP), and bis(2-di-iso-propylphosphinophenyl)phosphide (PPP). To better map the electronic coupling to copper, nitrogen, and phosphorus in these complexes, X-, S-, and Q-band EPR spectra have been obtained for each complex. The resulting EPR parameters implied by computer simulation are unusual for typical dicopper complexes and are largely consistent with previously published X-ray absorption spectroscopy and density functional theory data, where a highly covalent {Cu(2)(mu-XR(2))(2)}(+) diamond core has been assigned in which removal of an electron from the neutral {Cu(2)(mu-XR(2))(2)} can be viewed as ligand-centered to a substantial degree. To our knowledge, this is the first family of dicopper diamond core model complexes for which the compendium of X-, S-, and Q-band EPR spectra have been collected for comparison to Cu(A). PMID:19572723

  12. Novelty in the ESR process of making large hollow ingots

    NASA Astrophysics Data System (ADS)

    Medovar, L. B.; Stovpchenko, A. P.; Fedorovskii, B. B.

    2013-12-01

    The development of the formation of hollow ingots is briefly reviewed. The reasonability of application of large electroslag remelting hollow ingots, including the replacement of the forged and rolled metal of shells and rings by the low-deformed or even as-cast ESR metal, is shown. Data are presented on ESR of commercial hollow ingots produced by the remelting of short consumable electrodes exchanged in remelting.

  13. High resolution electron microscopy study of a high Cu variant of Weldalite (tm) 049 and a high strength Al-Cu-Ag-Mg-Zr alloy

    NASA Technical Reports Server (NTRS)

    Herring, R. A.; Gayle, Frank W.; Pickens, Joseph R.

    1991-01-01

    Weldalite (trademark) 049 is an Al-Cu-Li-Ag-Mg alloy that is strengthened in artificially aged tempers primarily by very thin plate-like precipitates lying on the set of (111) matrix planes. This precipitate might be expected to be the T(sub 1) phase, Al2CuLi, which has been observed in Al-Cu-Li alloys. However, in several ways this precipitate is similar to the omega phase which also appears as the set of (111) planes plates and is found in Al-Cu-Ag-Mg alloys. The study was undertaken to identify the set of (111) planes precipitate or precipitates in Weldalite (trademark) 049 in the T8 (stretched and artificially aged) temper, and to determine whether T(sub 1), omega, or some other phase is primarily responsible for the high strength (i.e., 700 MPa tensile strength) in this Al-Cu-Li-Ag-Mg alloy.

  14. Antiferromagnetism of La2CuO(4-y) studied by muon-spin rotation

    NASA Technical Reports Server (NTRS)

    Uemura, Y. J.; Kossler, W. J.; Yu, X. H.; Kempton, J. R.; Schone, H. E.

    1987-01-01

    Zero-field spin precession of positive muons has been observed in the antiferromagnetic state of La2CuO(4-y). Sharp onsets of the sublattice magnetization are found at temperatures close to those of the susceptibility maxima of different specimens. The long-lived precession signal indicates a microscopically homogeneous distribution of spin density at each Cu atom below the Neel temperature. A combination of the present results and neutron-scattering studies indicates the ordered moment per Cu atom to be significantly less than 1 mu(B).

  15. Atomic-scale studies on the effect of boundary coherency on stability in twinned Cu

    SciTech Connect

    Niu, Rongmei; Han, Ke Su, Yi-Feng; Salters, Vincent J.

    2014-01-06

    The stored energy and hardness of nanotwinned (NT) Cu are related to interaction between dislocations and (111)-twin boundaries (TBs) studied at atomic scales by high-angle annular dark-field scanning transmission electron microscope. Lack of mobile dislocations at coherent TBs (CTBs) provides as-deposited NT Cu a rare combination of stability and hardness. The introduction of numerous incoherent TBs (ITBs) reduces both the stability and hardness. While storing more energy in their ITBs than in the CTBs, deformed NT Cu also exhibits high dislocation density and TB mobility and therefore has increased the driving force for recovery, coarsening, and recrystallization.

  16. Surface science studies of catalyzed methanol synthesis on model copper and Cu-Zn-O surfaces

    SciTech Connect

    Fu, Sabrina Su-Bin . Dept. of Chemistry Lawrence Berkeley Lab., CA )

    1991-06-01

    Cu-Zn-O surfaces that are catalysts for methanol synthesis from CO, CO{sub 2}, and H{sub 2} modeled using zinc oxide overlayers on copper single crystals. These studies were performed in ultra-high vacuum (UHV) utilizing Temperature Programmed Desorption, Auger Electron Spectroscopy, and Low Energy Electron Diffraction techniques. The chemisorption of O{sub 2}, CO, CO{sub 2}, and D{sub 2} were compared on a stepped on Cu(311), and a flat Cu(110). At low pressures ({approximately}10{sup {minus}6} Torr), Cu(311) was found to be much more reactive than Cu(110) for the dissociative adsorption of CO{sub 2} and D{sub 2}, and the formation of CO{sub 2} from surface oxygen and CO. Since these reactions are important in methanol synthesis, these results suggest that methanol synthesis over copper may be a structure sensitive reaction. The interaction of copper, zinc, and oxygen were examined by the deposition of submonolayers to multilayers of zinc and oxygen in UHV on Cu(110). The interaction of methanol with these model Cu-Zn-O surfaces was also studied. Oxygen was adsorbed onto these exposed copper part of the surface to form ZnO{sub x}/y ML O/Cu(110) surfaces. The roles of ZnO{sub x} islands and chemisorbed oxygen on copper were investigated by monitoring methanol decomposition, into surface formate and methoxy species, on these ZnO{sub x}/y ML O/Cu(11) surfaces.

  17. Electronic properties of transition metal atoms on Cu2 N/Cu(100): a DFT comparative study

    NASA Astrophysics Data System (ADS)

    Ferron, Alejandro; Lado, José; Fernández-Rossier, Joaquín

    2015-03-01

    We study the electronic and magnetic properties of individual transition metal atoms (Ti, V, Cr, Mn, Fe, Co and Ni) deposited on a Cu2N /Cu(100) surface by means of spin-polarized density functional theory (DFT) calculations. We focus our work on a comparative study of the various quantities, such as magnetic moment, orbital occupation, structural properties, hybridization with the substrate and spin polarization of the substrate, paying attention to the trends as the transition metal is changed. In this work we try to go beyond existing theoretical works by providing a comprehensive and comparative study of the electronic, magnetic and structural properties of these seven atoms including also Ni, for which there are no published calculations to the best of our knowledge. In the case of Mn, Fe and Co, we connect our results with the existing scanning tunneling microscope experiments. A.F. acknowledges funding from the European Union's Seventh Framework Programme for research, technological development and demonstration, under the PEOPLE programme, Marie Curie COFUND Actions, grant agreement number 600375 and CONICET.

  18. Cell Cycle Regulation in the Estrogen Receptor Beta (ESR2)-Overexpressing Hep3B Hepatocellular Carcinoma Cell Line.

    PubMed

    Liu, Yi-Sheng; Tsai, Ying-Lan; Yeh, Yu-Lan; Chung, Li-Chin; Wen, Su-Ying; Kuo, Chia-Hua; Lin, Yueh-Min; Padma, V Vijaya; Kumar, V Bharath; Huang, Chih-Yang

    2015-04-30

    Epidemiological studies and experimental data have shown that the incidences of hepatocellular carcinoma in men are more frequent than in women. Evidence suggests that imbalance of hormones, including estrogen, androgen, prolactin, and growth hormone, modifies liver tumorigenesis. In this present study, we investigated how estrogen and estrogen receptor 2 (ESR2), regulates the cell cycle mechanism in Hep3B hepatocellular carcinoma cell line. Our results showed that ESR2 overexpression in the presence of 10⁻⁸ M 17-β-estradiol downregulated c-myc and cyclin D1 expression and simultaneously upregulated p27 expression. However, flow cytometry and MTT assays showed only minor G₁ phase arrest without affecting cell viability. Taken together, these observations indicate that ESR2 is required to lower tumorigenesis in males by altering cell cycle proteins in a ligand-dependent manner. PMID:25858474

  19. First-principles study of roles of Cu and Cl in polycrystalline CdTe

    DOE PAGESBeta

    Yang, Ji -Hui; Yin, Wan -Jian; Park, Ji -Sang; Metzger, Wyatt; Wei, Su -Huai

    2016-01-25

    In this study, Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance ptype doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu willmore » prefer to stay at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.« less

  20. Study of the superconducting properties of the Bi-Ca-Sr-Cu-O system

    NASA Technical Reports Server (NTRS)

    Khan, Musheer H.; Naqvi, S. M. M. R.; Zia-Ul-haq, S. M.

    1991-01-01

    High Temperature Superconductivity in the Bi-Ca-Sr-Cu-O System has been observed and has attracted considerable attention in 1988. The 80 K superconductivity phase has been identified to have a composition of Bi2CaSr2Cu2Ox, while the 110 K phase as reported in the literature has a possible composition of Bi2Ca2Sr2Cu3O(x). Researchers present here a study of the electrical properties of bulk samples of the slowly cooled and rapidly quenched 2:1:2:2 system. The samples used in this study were prepared from appropriate amounts of Bi2O3, CuO, SrCO3, CaCO3.

  1. Study of the superconducting properties of the Bi-Ca-Sr-Cu-O system

    NASA Technical Reports Server (NTRS)

    Khan, Musheer H.; Qidwai, A. A.; Zia-Ul-haq, S. M.; Binsaif, Rashid

    1990-01-01

    High Temperature Superconductivity in the Bi-Ca-Sr-Cu-O System has been observed and has attracted considerable attention in 1988. The 80 K superconductivity phase has been identified to have a composition of Bi2CaSr2Cu2Ox, while the 110 K phase as reported in the literature has a possible composition of Bi2Ca2Sr2Cu3Ox. Researchers present here a study of the electrical properties of bulk samples of the slowly cooled and rapidly quenched 2:1:2:2 system. The samples used in this study were prepared from appropriate amounts of Bi2O3, CuO, SrCO3, CaCO3.

  2. X-ray study of strains and dislocation density in epitaxial Cu/Ni/Cu/Si(001) films

    NASA Astrophysics Data System (ADS)

    Ha, K.; Ciria, M.; O'handley, R. C.; Stephens, P. W.; Pagola, S.

    1999-11-01

    The strain state of epitaxial Cu(50 Å)/Ni(tNi)/Cu(2000 Å)/Si(001) films as a function of the nickel film thickness (30 Å<=tNi<=2000 Å) has been studied using Bragg diffraction and grazing-incidence diffraction with a synchrotron x-ray source. For 30 Å<=tNi<=150 Å both the in-plane and out-of-plane nickel strains show a phenomenological (1/t)2/3 power dependence, which is significantly different from the 1/t law commonly accepted in the literature. The Matthews' theory, including the effect of the copper capping layer, is used to account for the equilibrium strains of the nickel layer. The 500 and 2000 Å films show larger strains than that predicted by the theory, consistent with other studies. The ratio of the nickel in-plane to out-of-plane strains is -1.18+/-0.05, very close to the expected nickel bulk value of -2c12/c11=-1.28.

  3. Systematic study of azimuthal anisotropy in Cu + Cu and Au + Au collisions at √sNN = 62.4 and 200 GeV

    SciTech Connect

    Adare, A.

    2015-09-23

    We have studied the dependence of azimuthal anisotropy v2 for inclusive and identified charged hadrons in Au+Au and Cu+Cu collisions on collision energy, species, and centrality. The values of v2 as a function of transverse momentum pT and centrality in Au+Au collisions at √sNN=200 and 62.4 GeV are the same within uncertainties. However, in Cu+Cu collisions we observe a decrease in v2 values as the collision energy is reduced from 200 to 62.4 GeV. The decrease is larger in the more peripheral collisions. By examining both Au+Au and Cu+Cu collisions we find that v2 depends both on eccentricity and the number of participants, Npart. We observe that v2 divided by eccentricity (ε) monotonically increases with Npart and scales as N1/3part. Thus, the Cu+Cu data at 62.4 GeV falls below the other scaled v2 data. For identified hadrons, v2 divided by the number of constituent quarks nq is independent of hadron species as a function of transverse kinetic energy KET=mT–m between 0.1T/nq<1 GeV. Combining all of the above scaling and normalizations, we observe a near-universal scaling, with the exception of the Cu+Cu data at 62.4 GeV, of v2/(nq∙ε∙N1/3part) vs KET/nq for all measured particles.

  4. Systematic study of azimuthal anisotropy in Cu + Cu and Au + Au collisions at √sNN = 62.4 and 200 GeV

    DOE PAGESBeta

    Adare, A.

    2015-09-23

    We have studied the dependence of azimuthal anisotropy v2 for inclusive and identified charged hadrons in Au+Au and Cu+Cu collisions on collision energy, species, and centrality. The values of v2 as a function of transverse momentum pT and centrality in Au+Au collisions at √sNN=200 and 62.4 GeV are the same within uncertainties. However, in Cu+Cu collisions we observe a decrease in v2 values as the collision energy is reduced from 200 to 62.4 GeV. The decrease is larger in the more peripheral collisions. By examining both Au+Au and Cu+Cu collisions we find that v2 depends both on eccentricity and themore » number of participants, Npart. We observe that v2 divided by eccentricity (ε) monotonically increases with Npart and scales as N1/3part. Thus, the Cu+Cu data at 62.4 GeV falls below the other scaled v2 data. For identified hadrons, v2 divided by the number of constituent quarks nq is independent of hadron species as a function of transverse kinetic energy KET=mT–m between 0.1T/nq<1 GeV. Combining all of the above scaling and normalizations, we observe a near-universal scaling, with the exception of the Cu+Cu data at 62.4 GeV, of v2/(nq∙ε∙N1/3part) vs KET/nq for all measured particles.« less

  5. Implication of the estrogen receptors GPER, ESR1, ESR2 in post-testicular maturations of equine spermatozoa.

    PubMed

    Gautier, Camille; Barrier-Battut, Isabelle; Guénon, Isabelle; Goux, Didier; Delalande, Christelle; Bouraïma-Lelong, Hélène

    2016-07-01

    Estrogen receptors ESR1, ESR2 and GPER are present on mature ejaculated horse spermatozoa, suggesting these cells as putative targets for estrogens. Indeed, spermatozoa are exposed to high level of estrogens during the transit in the male and female genital tracts but their roles are not investigated. So, we evaluated in vitro the role of 17β-estradiol during post-testicular maturations: regulation of motility, capacitation and acrosome reaction. Moreover according to the pseudo-seasonal breeder status of the stallion, we analyzed the putative seasonal variations in the presence of ESRs in spermatozoa. We showed that ESRs are more present on stallion sperm during the breeding season. We showed that capacitation and acrosome reaction are independent of estradiol action in horse. Estradiol can weakly modulate the motility and this effect is strictly associated with GPER and not with ESR1 and ESR2. The subcellular localization of GPER in the neck on stallion sperm is coherent with this effect. It seems that estrogens are not major regulators of sperm maturations associated to mare genital tract, so they could act during the epididymal maturations. PMID:27222348

  6. Temperature dependence diode parameters studies of Al/CuPc/n-Si/Al structure

    NASA Astrophysics Data System (ADS)

    Kumar, Ratnesh; Kaur, Ramneek; Sharma, Mamta; Kaur, Maninder; Tripathi, S. K.

    2015-08-01

    This paper presents the fabrication of Al/CuPc/n-Si/Al metal-organic-semiconductor diode. The copper phthalocyanine as organic layer is deposited on Si substrate by thermal evaporation technique. The temperature dependent current-voltage measurements are performed on Al/CuPc/n-Si structure. The important diode parameters i.e. the barrier height and ideality factor have been calculated. The temperature dependence of barrier height and ideality factor has been studied.

  7. Synthesis, characterization and equilibrium studies of some potential antimicrobial and antitumor complexes of Cu(II), Ni(II), Zn(II) and Cd(II) ions involving 2-aminomethylbenzimidazole and glycine

    NASA Astrophysics Data System (ADS)

    Aljahdali, M.

    2013-08-01

    The ternary complexes of Cu(II), Zn(II), Ni(II) and Cd(II) with 2-aminomethylbenzimidazole (AMBI) and glycine as a representative example of amino acids have been isolated and characterized by elemental analyses, IR, ESR, UV-vis, magnetic moment, molar conductance and 1H NMR spectra. AMBI behaves as neutral bidentate ligands with coordination through imidazole and amino group nitrogens while the glycine amino acid behaves as a monodenate anion with coordination involving the amino group and carboxylate oxygen after deprotonation. The magnetic and spectral data indicates a square planar geometry for both Cu2+ and Ni2+ complexes and a tetrahedral geometry for both Zn2+ and Cd2+ complexes. The isolated chelates have been screened for their antifungal and antibacterial activities using the disc diffusion method. A cytotoxicity of the compounds against colon (HCT116) and larynx (HEP2) cancer cells have been studied. The stability constants of ternary M-AMBI-Gly complexes were determined potentiometrically in aqueous solution at I = 0.1 mol dm-3 NaCl.

  8. Investigation of the H-Cu and Cu-Cu bonds in hydrogenated Cu

    NASA Astrophysics Data System (ADS)

    Shuttleworth, I. G.

    2013-01-01

    The pure and hydrogenated copper system CuHn (n=0, 0.25, 0.50, 0.75 and 1) has been investigated using LCAO-DFT. The average H-Cu (Cu-Cu) bonding interaction increases (decreases) with n whilst concurrent orbital-resolved studies of the H-Cu interactions showed that the (non-)directional H-Cu bonds become more (less) bonding. This preference for directional bonds is reflected in the Cu-Cu interactions. CuH0.25 is shown to have an unusually localized electronic structure compared to the more hydrogenated systems, and the origins of this structure are discussed.

  9. Comparative Study of the Defect Point Physics and Luminescence of the Kesterites Cu2ZnSnS4 and Cu2ZnSnSe4 and Chalcopyrite Cu(In,Ga)Se2: Preprint

    SciTech Connect

    Romero, M. J.; Repins, I.; Teeter, G.; Contreras, M.; Al-Jassim, M.; Noufi, R.

    2012-08-01

    In this contribution, we present a comparative study of the luminescence of the kesterites Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) and their related chalcopyrite Cu(In,Ga)Se2 (CIGSe). Luminescence spectroscopy suggests that the electronic properties of Zn-rich, Cu-poor kesterites (both CZTS and CZTSe) and Cu-poor CIGSe are dictated by fluctuations of the electrostatic and chemical potentials. The large redshift in the luminescence of grain boundaries in CIGSe, associated with the formation of a neutral barrier is clearly observed in CZTSe, and, to some extent, in CZTS. Kesterites can therefore replicate the fundamental electronic properties of CIGSe.

  10. Electronic structure of copper halides CuI and CuCl: A comparative X-Ray photoelectron and absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Generalov, A. V.; Vinogradov, A. S.

    2013-06-01

    The energy distributions of the occupied and unoccupied electronic states for copper halides CuCl and CuI have been investigated using X-ray photoemission and absorption spectroscopy with a highenergy resolution on the equipment of the Russian-German beamline for outlet and monochromatization of synchrotron radiation from the electron storage ring BESSY II. A quasi-molecular analysis of the obtained experimental spectra has revealed that there is a fundamental similarity of the energy structures of the valence band and the conduction band of copper halides Cu X ( X = Cl, I) due to the identical atomic structure of the studied compounds. The differences in the positions of individual energy subbands in the valence band and the conduction band of Cu X and in their intensities in the spectra are associated with different degrees of hybridization of the Cu 3 d, 4 s and X( n + 1) s, np valence states, as well as with different sizes of structural units (CuCl4 and CuI4 quasi-molecules) of the studied crystals.

  11. Electroslag Remelting (ESR) Slags for Removal of Radioactive Oxide Contaminants from Stainless Steel, Annual Report (1998-1999)

    SciTech Connect

    PAL, UDAY B.

    1999-08-01

    Decontamination of radioactive contaminated stainless steel using the ESR process is investigated by conducting thermophysical and thermochemical laboratory studies on the slag. The ESR base slag investigated in this research project is 60wt%CaF{sub 2}-20wt%CaO-20wt%Al{sub 2}O{sub 3}. In this report, we present the data obtained to date on relevant slag properties, capacity to incorporate the radioactive contaminant (using CeO{sub 3}) as surrogate, simulant for PUO{sub 2} and UO{sub 2}, slag-metal partition coefficient, volatilization rate and volatile species, viscosity, electrical conductivity and surface tension as a function of temperature. The impact of these properties on the ESR decontamination process is presented.

  12. The Luminescence and ESR of a Synthetic Emerald and the Natural Ones Mined from Santa Terezinha in Brazil

    NASA Astrophysics Data System (ADS)

    Ohkura, Hiroshi; Hashimoto, Hisashi; Mori, Yuzo; Chiba, Yoshinori; Isotani, Sadao

    1987-09-01

    Both the luminescence and ESR of a synthetic (KC-) emerald and a natural (ST-) type, mined from Santa Terezinha in Brazil, have been studied. The luminescence spectra of the impurity Cr3+ ions in both emeralds consist of two zerophonon lines followed by satellite bands. The satellite band of the ST-emerald shows huge intensity and broad width compared with that of the KC-emerald. The ESR of the Cr3+ ions in the ST-emerald is specific in the anisotropy of the g-factor and has a wider peak-to-peak value than the KC-emerald. We propose that these differences are caused by an interaction induced by the presence of a large number of impurity Fe3+ ions contained in the ST-emerald. The existence of Fe3+ and their concentrations were estimated by ESR.

  13. ESR signals in a core from the lake Baikal: implications for climate change

    NASA Astrophysics Data System (ADS)

    Toyoda, S.; Hidaka, K.; Takamatsu, N.

    2002-12-01

    Electron spin resonance dating method has been used for obtaining ages of Quaternary events using speleothem, corals, shells, hydroxyapatite in tooth enamel, gypsum, and quartz (Ikeya, 1993). Recently, it was also found that an ESR signal in quartz of loess is useful to discuss the variation of its origin (e. g. Ono et al., 1998). The method is based on the signal intensity of the heat treated (gamma ray irradiation and heating, Toyoda and Ikeya, 1991) E 1_f center (an unpaired electron at an oxygen vacancy) correlates the original (crystallization) age of quartz (e.g. Toyoda and Hattori, 2000). If there is variation in ages of basement rocks (origin of loess), ESR signal intensity may differentiate the origins. We applied the present method to sediments taken from the core of the lake Baikal with the length of 600m. The ESR intensity of the heat treated E1_f center was determined by an ESR measurement at room temperature for about 100 mg of the bulk samples, with a microwave power of 0.01 mW, field modulation amplitude of 0.1 mT, and with a scan range of 5 mT around g=2.001 after gamma ray irradiation to 1 kGy and subsequent heating at 300C. The ESR signal of the E1_f center was clearly observed although other minerals are also included in the bulk sample. The peak to peak height was taken as the signal intensity after normalizing the height with the gain (the instrumental setting at the time of measurement), mass, and the intensity of the standard simultaneously measured with the sample. The concentrations of the quartz in the bulk samples were obtained by the X ray diffraction study, normalizing the peak intensity with a standard CeO sample. The variation of the ESR signal intensity with depth of the core will be presented together with the possible climate change which may have caused the variation. References M. Ikeya (1993) New applications of electron spin resonance, dating, dosimetry and imaging, World Scientific. Y. Ono, T. Naruse, M. Ikeya, H. Kohno, and

  14. Diffusion of small two-dimensional Cu islands on Cu(111) studied with a kinetic Monte Carlo method

    NASA Astrophysics Data System (ADS)

    Karim, Altaf; Al-Rawi, Ahlam N.; Kara, Abdelkader; Rahman, Talat S.; Trushin, Oleg; Ala-Nissila, Tapio

    2006-04-01

    Diffusion of small two-dimensional Cu islands (containing up to 10 atoms) on Cu(111) has been studied using the newly developed self-learning Kinetic Monte Carlo (SLKMC) method which is based on a database of diffusion processes and their energetics accumulated automatically during the implementation of the SLKMC code. Results obtained from simulations in which atoms hop from one fcc hollow site to another are compared with those obtained from a parallel set of simulations in which the database is supplemented by processes revealed in complementary molecular dynamics simulations at 500K . They include processes involving the hcp (stacking-fault) sites, which facilitate concerted motion of the islands (simultaneous motion of all atoms in the island). A significant difference in the scaling of the effective diffusion barriers with island size is observed in the two cases. In particular, the presence of concerted island motion leads to an almost linear increase in the effective diffusion barrier with size, while its absence accounts for strong size-dependent oscillations and anomalous behavior for trimers and heptamers. We also identify and discuss in detail the key microscopic processes responsible for the diffusion and examine the frequencies of their occurrence, as a function of island size and substrate temperature.

  15. Photoelectron spectroscopic and computational study of (M-CO2)- anions, M = Cu, Ag, Au

    NASA Astrophysics Data System (ADS)

    Zhang, Xinxing; Lim, Eunhak; Kim, Seong K.; Bowen, Kit H.

    2015-11-01

    In a combined photoelectron spectroscopic and computational study of (M-CO2)-, M = Au, Ag, Cu, anionic complexes, we show that (Au-CO2)- forms both the chemisorbed and physisorbed isomers, AuCO 2- and Au-(CO2), respectively; that (Ag-CO2)- forms only the physisorbed isomer, Ag-(CO2); and that (Cu-CO2)- forms only the chemisorbed isomer, CuCO 2- . The two chemisorbed complexes, AuCO 2- and CuCO 2- , are covalently bound, formate-like anions, in which their CO2 moieties are significantly reduced. These two species are examples of electron-induced CO2 activation. The two physisorbed complexes, Au-(CO2) and Ag-(CO2), are electrostatically and thus weakly bound.

  16. First-principles study of roles of Cu and Cl in polycrystalline CdTe

    NASA Astrophysics Data System (ADS)

    Yang, Ji-Hui; Yin, Wan-Jian; Park, Ji-Sang; Metzger, Wyatt; Wei, Su-Huai

    2016-01-01

    Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance p-type doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu will prefer to stay at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.

  17. In vivo dose evaluation during gynaecological radiotherapy using L-alanine/ESR dosimetry.

    PubMed

    Rech, Amanda Burg; Barbi, Gustavo Lazzaro; Ventura, Luiz Henrique Almeida; Guimarães, Flavio Silva; Oliveira, Harley Francisco; Baffa, Oswaldo

    2014-06-01

    The dose delivered by in vivo 3-D external beam radiation therapy (EBRT) was verified with L-alanine/electron spin resonance (ESR) dosimetry for patients diagnosed with gynaecological cancer. Measurements were performed with an X-band ESR spectrometer. Dosemeters were positioned inside the vaginal cavity with the assistance of an apparatus specially designed for this study. Previous phantom studies were performed using the same conditions as in the in vivo treatment. Four patients participated in this study during 20-irradiation sessions, giving 220 dosemeters to be analysed. The doses were determined with the treatment planning system, providing dose confirmation. The phantom study resulted in a deviation between -2.5 and 2.1 %, and for the in vivo study a deviation between -9.2 and 14.2 % was observed. In all cases, the use of alanine with ESR was effective for dose assessment, yielding results consistent with the values set forth in the International Commission on Radiation Units and Measurements (ICRU) reports. PMID:24751984

  18. Theoretical studies on the Knight shifts for the tetragonal Cu2+ site in HgBa2CuO4+δ

    NASA Astrophysics Data System (ADS)

    Li, Guo-Liang; Wu, Shao-Yi; Kuang, Min-Quan; Hu, Xian-Fen

    2015-08-01

    The Knight shifts for the tetragonal Cu2+ site in HgBa2CuO4+δ are theoretically studied from the high order perturbation formulas of the Knight shifts for a tetragonally elongated octahedral 3d9 cluster. The significant anisotropy of the Knight shifts is attributable to the obvious tetragonal elongation distortion of the Cu2+ site. The anisotropic g factors of this system are uniformly analyzed, and the calculation results and the local structure of the copper site are also discussed.

  19. Theoretical study of the X 2Pi and A 2Sigma(+) states of CuO and CuS

    NASA Technical Reports Server (NTRS)

    Langhoff, S. R.; Bauschlicher, C. W., Jr.

    1986-01-01

    Theoretical spectroscopic constants and dipole moments are determined for the X 2Pi and A 2Sigma(+) states of CuO and CuS, using extended Gaussian basis sets and incorporating correlation using both configuration interaction (CI) and coupled pair (CPF) methods. Relativistic corrections (Darwin plus mass velocity), included using first-order perturbation theory, are found to be relatively small. At the CPF level, significant configuration mixing with the 3d(9)4s(1) occupation occurs for both states, resulting in some bond shortening and a significant increase in the dissociation energy. The best spectroscopic parameters are in excellent agreement with experiment for both CuO and CuS. In analogy with CuO, CuS is predicted to have a yet unobserved 2Sigma(+) state near 10,000 per cm.

  20. {sup 63}Cu and {sup 115}In NMR study of CuInS{sub 2} semiconductor

    SciTech Connect

    Khabibullin, I. Kh. Matukhin, V. L. Ermakov, V. L.; Gnezdilov, O. I.; Korzun, B. V.; Schmidt, E. V.

    2009-01-15

    Two CuInS{sub 2} semiconductor samples synthesized from chemical elements with the equiatomic cation ratio (N{sub Cu}/N{sub In} = 1) and either an excess or stoichiometric sulfur content have been investigated by {sup 63}Cu and {sup 115}In nuclear magnetic resonance. The spectra were recorded on a Bruker Avance-400 spectrometer at a temperature of 290 K and frequencies of 106.14 MHz ({sup 63}Cu) and 87.67 MHz ({sup 115}In). Numerical simulation made it possible to determine the quadrupole coupling constants: 0.34 MHz ({sup 63}Cu) and 1.1 MHz ({sup 115}In). For the samples synthesized with excess sulfur (above stoichiometry), distortions are revealed in both the {sup 63}Cu and {sup 115}In spectra.

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

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Li, N.; Bufford, D. C.; Li, J.; Hattar, K.; Wang, H.; Zhang, X.

    2016-07-01

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

  2. Nuclear astrophysics experiments with stored, highly-charged ions at FRS-ESR at GSI

    SciTech Connect

    Scheidenberger, Christoph

    2010-08-12

    At the FRS-ESR complex of GSI a nuclear physics program with exotic nuclei has been established in last 18 years, which also addresses key questions and nuclear properties relevant in nuclear astrophysics. The paper summarizes production of exotic nuclei, lifetime studies of highly-charged ions, direct mass measurements and reactions at internal targets. A few comments on the analysis of two-body weak decays are given.

  3. Liquid-phase ESR, ENDOR, and TRIPLE resonance of porphycene anion radicals

    SciTech Connect

    Schluepmann, J.; Huber, M.; Plato, M.; Moebius, K. ); Toporowicz, M.; Levanon, H. ); Koecher, M.; Vogel, E. )

    1990-08-29

    Porphycenes are novel structural isomers of porphyrins. The radical anions of several porphycenes were studied by ESR, ENDOR, and TRIPLE resonance in liquid solution yielding the isotropic hyperfine coupling constants including signs. For the unsubstituted free-base porphycene, the 2,7,12,17-tetra-n-propylporphycene, and the 9,10,19,20-tetra-n-propylporphycene, the experimental findings are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/SP).

  4. ESR, U-series and paleomagnetic dating of Gigantopithecus fauna from Chuifeng Cave, Guangxi, southern China

    NASA Astrophysics Data System (ADS)

    Shao, Qingfeng; Wang, Wei; Deng, Chenglong; Voinchet, Pierre; Lin, Min; Zazzo, Antoine; Douville, Eric; Dolo, Jean-Michel; Falguères, Christophe; Bahain, Jean-Jacques

    2014-07-01

    Several Gigantopithecus faunas associated with taxonomically undetermined hominoid fossils and/or stone artifacts are known from southern China. These faunas are particularly important for the study of the evolution of humans and other mammals in Asia. However, the geochronology of the Gigantopithecus faunas remains uncertain. In order to solve this problem, a program of geochronological studies of Gigantopithecus faunas in Guangxi Province was recently initiated. Chuifeng Cave is the first studied site, which yielded 92 Gigantopithecus blacki teeth associated with numerous other mammalian fossils. We carried out combined ESR/U-series dating of fossil teeth and sediment paleomagnetic studies. Our ESR results suggest that the lower layers at this cave can be dated to 1.92 ± 0.14 Ma and the upper layers can be dated to older than 1.38 ± 0.17 Ma. Correlation of the recognized magnetozones to the geomagnetic polarity timescale was achieved by combining magnetostratigraphic, biostratigraphic and ESR data. The combined chronologies establish an Olduvai subchron (1.945-1.778 Ma) for the lowermost Chuifeng Cave sediments. We also analyzed the enamel δ13C values of the Gigantopithecus faunas. Our results show that southern China was dominated by C3 plants during the early Pleistocene and that the Gigantopithecus faunas lived in a woodland-forest ecosystem.

  5. Comparative study of flux pinning, creep and critical currents between YBaCuO crystals with and without Y2BaCuO5 inclusions

    NASA Technical Reports Server (NTRS)

    Murakami, Masato; Gotoh, Satoshi; Fujimoto, Hiroyuki; Koshizuka, Naoki; Tanaka, Shoji

    1991-01-01

    In the Y-Ba-Cu-O system, YBa2Cu3O(x) phase is produced by the following peritectic reaction: Y2BaCuO5 + liquid yields 2YBa2Cu3O(x). Through the control of processing conditions and starting compositions, it becomes possible to fabricate large crystals containing fine Y2BaCuO5(211) inclusions. Such crystals exhibit Jc values exceeding 10000 A/sq cm at 77 K and 1T. Recently, researchers developed a novel process which can control the volume fraction of 211 inclusions. Elimination of 211 inclusions is also possible. In this study, researchers prepared YBaCuO crystals with and without 211 inclusions using the novel process, and compared flux pinning, flux creep and critical currents. Magnetic field dependence of Jc for YBaCuO crystals with and with 211 inclusions is shown. It is clear that fine 211 inclusions can contribute to flux pinning. It was also found that flux creep rate could be reduced by increasing flux pinning force. Critical current density estimates based on the conventional flux pinning theory were in good agreement with experimental results.

  6. Comparative study of flux pinning flux creep and critical currents between YBaCuO crystals with and without Y2BaCuO5 inclusions

    NASA Technical Reports Server (NTRS)

    Murakami, Masato; Gotoh, Satoshi; Fujimoto, Hiroyuki; Koshizuka, Naoki; Tanaka, Shoji

    1990-01-01

    In the Y-Ba-Cu-O system YBa2Cu3Ox phase is produced by the following peritectic reaction: Y2BaCuO5 + liquid yields 2YBa2Cu3Ox. Through the control of processing conditions and starting compositions it becomes possible to fabricate large crystals containing fine Y2BaCuO5(211) inclusions. Such crystals exhibit Jc values exceeding 10000 A/sq cm at 77 K and 1T. Recently, researchers developed a novel process which can control the volume fraction of 211 inclusions. Elimination of 211 inclusions is also possible. In this study, researchers prepared YBaCuO crystals with and without 211 inclusions using the novel process and compared flux pinning, flux creep and critical currents. Magnetic field dependence of Jc for YBaCuO crystals with and without 211 inclusions is shown. It is clear that fine 211 inclusions can contribute to flux pinning. It was also found that flux creep rate could be reduced by increasing flux pinning force. Critical current density estimates based on the conventional flux pinning theory were in good agreement with experimental results.

  7. NO dissociation on Cu(111) and Cu2O(111) surfaces: a density functional theory based study

    NASA Astrophysics Data System (ADS)

    Padama, A. A. B.; Kishi, H.; Arevalo, R. L.; Moreno, J. L. V.; Kasai, H.; Taniguchi, M.; Uenishi, M.; Tanaka, H.; Nishihata, Y.

    2012-05-01

    NO dissociation on Cu(111) and Cu2O(111) surfaces is investigated using spin-polarized density functional theory. This is to verify the possibility of using Cu-based catalyst for NO dissociation which is the rate limiting step for the NOx reduction process. The dissociation of molecularly adsorbed NO on the surface is activated for both cases. However, from the reaction path of the NO-Cu2O(111) system, the calculated transition state lies below the reference energy which indicates the possibility of dissociation. For the NO-Cu(111) system, the reaction path shows that NO desorption is more likely to occur. The geometric and electronic structure of the Cu2O(111) surface indicates that the surface Cu atoms stabilize themselves with reference to the O atom in the subsurface. The interaction results in modification of the electronic structure of the surface Cu atoms of Cu2O(111) which greatly affects the adsorption and dissociation of NO. This phenomenon further explains the obtained differences in the dissociation pathways of NO on the surfaces.

  8. Combined Laser and Electron Cooling of Bunched C3+ Ion Beams at the Storage Ring ESR

    SciTech Connect

    Schramm, U.; Bussmann, M.; Habs, D.; Kuehl, T.; Beller, P.; Franzke, B.; Nolden, F.; Steck, M.; Saathoff, G.; Reinhardt, S.; Karpuk, S.

    2006-03-20

    We report on first laser cooling studies of bunched beams of triply charged carbon ions stored at an energy of 1.46 GeV at the ESR (GSI). Despite for the high beam energy and charge state laser cooling provided a reduction of the momentum spread of one order of magnitude in space-charge dominated bunches as compared to electron cooling. For ion currents exceeding 10 {mu}A intra-beam-scattering losses could not be compensated by the narrow band laser system presently in use. Yet, no unexpected problems occurred encouraging the envisaged extension of the laser cooling to highly relativistic beams. At ESR, especially the combination with modest electron cooling provided three-dimensionally cold beams in the plasma parameter range of unity, where ordering effects can be expected and a still unexplained signal reduction of the Schottky signal is observed.

  9. Spin probe dynamics in relation to free volume in crystalline organics from ESR and PALS: Cyclohexane

    NASA Astrophysics Data System (ADS)

    Švajdlenková, H.; Zgardzinska, B.; Lukešová, M.; Bartoš, J.

    2016-01-01

    A joint external probe ESR and PALS study on cyclohexane (CHX) using stable free radical 2,2,6,6-tetra-methyl-1-piperidinyloxy (TEMPO) or ortho-positronium (o-Ps), respectively, is reported. The slow to fast transition of TEMPO occurs at the characteristic ESR temperature T50G coinciding with the solid to solid transition temperature, TSS. Moreover, o-Ps lifetime τ3(T50G) = 2.0 ns is close to an empirical rule τ3(T50G) = 2.17 ± 0.15 ns found for a series of amorphous glass-formers indicating that main transition of the TEMPO connected with the 'rigid' to plastic crystalline state transition in CHX occurs under the similar local free volume condition as in amorphous media.

  10. Spin Doublet Point Defects in Graphenes: Predictions for ESR and NMR Spectral Parameters.

    PubMed

    Vähäkangas, Jarkko; Lantto, Perttu; Mareš, Jiří; Vaara, Juha

    2015-08-11

    An adatom on a graphene surface may carry a magnetic moment causing spin-half paramagnetism. This theoretically predicted phenomenon has recently also been experimentally verified. The measurements of defect-induced magnetism are mainly based on magnetometric techniques where artifacts such as environmental magnetic impurities are hard to rule out. Spectroscopic methods such as electron spin resonance (ESR) and paramagnetic nuclear magnetic resonance (pNMR) are conventionally used in the development of magnetic materials, e.g., to study paramagnetic centers. The present density functional theory study demonstrates with calculations of the ESR g-tensor and the hyperfine coupling tensors, as well as the pNMR shielding tensor, that these spectroscopies can be used to identify the paramagnetic centers in graphenes. The studied defects are hydrogen and fluorine adatoms on sp(2)-hybridized graphene, as well as hydrogen and fluorine vacancies in the sp(3)-hybridized graphane and fluorographene, respectively. The directly measurable ESR and pNMR parameters give insight into the electronic and atomic structures of these defects and may contribute to understanding carbon-based magnetism via the characterization of the defect centers. We show that missing hydrogen and fluorine atoms in the functionalized graphane and fluorographene, respectively, constitute sp(2)-defect centers, in which the magnetic resonance parameters are greatly enhanced. Slowly decaying adatom-induced magnetic resonance parameters with the distance from the sp(3)-defect, are found in pure graphene. PMID:26574457

  11. Spin Labeling ESR Investigation of Covalently Bound Residues in Soil

    NASA Astrophysics Data System (ADS)

    Aleksandrova, Olga; Steinhoff, Heinz-Juergen; Klasmeier, Joerg; Schulz, Marcus; Matthies, Michael

    2013-04-01

    Organic xenobiotic chemicals, such as pesticides, biocides and veterinary pharmaceuticals, interact with soil, which results in the simultaneous formations of metabolites, mineralization products, and bound or non-extractable residues (NER). Substances or metabolites with reactive functional groups, such as aniline or phenol, have a tendency to give a larger proportion of NER. Despite numerous studies on NER, the majority of their chemical structures is still unknown. Reversible sequestration and irreversible formation of NER were also observed for veterinary antibiotic pharmaceuticals, after their application to soil with and without manure. For this purpose, we hypothesized a key role of specific functional groups of soil contaminants, via which contaminants are covalently bound to soil constituents, and advance a method of spin labeling ESR investigation of reaction products using a membrane method. Spin labels (SL) represent chemically stable paramagnetic molecules used as molecular labels and molecular probes for testing the covalent binding, structural properties, and molecular mobility of different physical, chemical, and biological systems. In the case of covalent binding of SL, their ESR spectra become broadened. We used stable nitroxide radicals (NR) as SL. These radicals modeled organic chemical contaminants and differed only in one functional group. The paramagnetic SL 4-Amino Tempo (4-amino-2,2,6,6-tetramethyl-1-piperidinylox) differed from Tempo (2,2,6,6-Tetramethylpiperidinooxy) in a substituent at the para-position of the piperidine ring, whereas Aniline Tempo (1-Piperidinyloxy, 2,2,6,-tetramethyl, 6-Aniline) differed from Tempo in an Aniline substituting one CH3 functional group. Before experimental analysis, we tested temporal changes in the concentration of both NR incubated with soil and found that the life-times of them in soil exceeded 3 days. We contaminated and labeled soil samples with NR, adding to soil the aqueous solution, which already

  12. Active phase of a Pd-Cu/ZSM-5 catalyst for benzene hydroxylation: In-situ XAFS studies

    NASA Astrophysics Data System (ADS)

    Cho, Kye-Sung; Lee, Yong-Kul

    2012-07-01

    The gas-phase hydroxylation of benzene by using a mixture of oxygen and hydrogen has been carried out over Cu/ZSM-5 catalysts modified with palladium. In-situ X-ray absorption studies employed in the course of H2-tempereature programmed reduction (H2-TPR) followed by benzene hydroxylation confirmed that the oxidic phase of Cu2+ was transformed to Cu+ during the reaction. The addition of Pd to Cu/ZSM-5 noticeably improved the reducibility of the oxidic Cu phase, which resulted in an increase in the activity of the reaction.

  13. XPS and Raman study of slope-polished Cu(In,Ga)Se2 thin films

    NASA Astrophysics Data System (ADS)

    Beak, Gun Yeol; Jeon, Chan-Wook

    2016-05-01

    The growth of quality Cu(In,Ga)Se2 photovoltaic absorber without secondary phases is very important for improving the solar cell efficiency. Although X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy can identify the secondary phases, they provide insufficient information because of their insufficient resolution and complexity in analysis. In general, normal Raman spectroscopy is better for the analysis of secondary phases. On the other hand, the Raman signal provides information for film depths of less than 300 nm, and the Raman information cannot represent the properties of the entire film. In this regard, the authors introduce a new way of identifying secondary phases in Cu(In,Ga)Se2 films using depth Raman analysis. The as-prepared film was polished using a dimple grinder, which expanded a 2 μm thick film to approximately 1 mm, which is more than sufficient to resolve the depth distribution. Raman analysis indicated that the Cu(In,Ga)Se2 film showed different secondary phases, such as CuIn3Se5, InSe and CuSe, present in different depths of the film, whereas XPS provided complex information about the phases. Overall, the present study emphasizes that the Raman depth profile is more efficient for the identification of secondary phases in Cu(In,Ga)Se2 thin films than XPS and XRD. [Figure not available: see fulltext.

  14. In vitro study on an antibacterial Ti-5Cu alloy for medical application.

    PubMed

    Ma, Zheng; Li, Mei; Liu, Rui; Ren, Ling; Zhang, Yu; Pan, Haobo; Zhao, Ying; Yang, Ke

    2016-05-01

    Health of human beings is subjected to severe threats from the spread of harmful bacteria and the implant-associated infection remains a serious problem in clinic. In this study, a copper-bearing antibacterial titanium alloy, Ti-5Cu, has been developed for dental and orthopedic implant applications. The microstructure, mechanical property, electrochemical corrosion behavior, in vitro antibacterial performance, cytocompatibility and hemocompatibility of the alloy are systematically investigated. The results reveal that the Ti-5Cu alloy which consists of α-phase matrix and intermetallic compound Ti2Cu not only possesses strong antibacterial activity against both E. coli and S. aureus, but also exhibits better mechanical properties than the commercial pure titanium. It is confirmed that the release of trace amount of Cu ions from the alloy plays an important role in killing bacteria. In spite of the ion release, Ti-5Cu alloy still reveals excellent corrosion resistance. Moreover, good cytocompatibility and superior hemocompatibility make Ti-5Cu alloy to be a potential solution that could prevent the peri-implant infection in dental and orthopaedic applications. PMID:26975748

  15. Reducing inappropriate ESR testing with computerized clinical decision support

    PubMed Central

    Gottheil, Stephanie; Khemani, Ekta; Copley, Katherine; Keeney, Michael; Kinney, Jeff; Chin-Yee, Ian; Gob, Alan

    2016-01-01

    Laboratory test overutilization increases health care costs, leads to unwarranted investigations, and may have a negative impact on health outcomes. The American Society of Clinical Pathology, in its Choosing Wisely Campaign, advocates that inflammation be investigated with C-reactive protein (CRP) instead of Erythrocyte Sedimentation Rate (ESR). London Health Sciences Centre (LHSC), a tertiary care hospital organization in Ontario, Canada, set a goal to reduce inappropriate ESR orders by 50%. After developing appropriateness criteria for ESR, we used a series of PDSA cycles to reduce inappropriate ESR ordering and analyzed our results with an interrupted time series design. Our intervention began with an educational bulletin and moved to city-wide implementation of computerized Clinical Decision Support (CDS). After implementation, ESR orders decreased by 40% from 386 orders per week to 241 orders per week. Our results are supported by previous literature on the effectiveness of CDS in reducing overutilization and suggest that provider habit is a significant contributor to inappropriate ordering. PMID:27096092

  16. Reducing inappropriate ESR testing with computerized clinical decision support.

    PubMed

    Gottheil, Stephanie; Khemani, Ekta; Copley, Katherine; Keeney, Michael; Kinney, Jeff; Chin-Yee, Ian; Gob, Alan

    2016-01-01

    Laboratory test overutilization increases health care costs, leads to unwarranted investigations, and may have a negative impact on health outcomes. The American Society of Clinical Pathology, in its Choosing Wisely Campaign, advocates that inflammation be investigated with C-reactive protein (CRP) instead of Erythrocyte Sedimentation Rate (ESR). London Health Sciences Centre (LHSC), a tertiary care hospital organization in Ontario, Canada, set a goal to reduce inappropriate ESR orders by 50%. After developing appropriateness criteria for ESR, we used a series of PDSA cycles to reduce inappropriate ESR ordering and analyzed our results with an interrupted time series design. Our intervention began with an educational bulletin and moved to city-wide implementation of computerized Clinical Decision Support (CDS). After implementation, ESR orders decreased by 40% from 386 orders per week to 241 orders per week. Our results are supported by previous literature on the effectiveness of CDS in reducing overutilization and suggest that provider habit is a significant contributor to inappropriate ordering. PMID:27096092

  17. CRYRING@ESR: present status and future research

    NASA Astrophysics Data System (ADS)

    Lestinsky, M.; Bräuning-Demian, A.; Danared, H.; Engström, M.; Enders, W.; Fedotova, S.; Franzke, B.; Heinz, A.; Herfurth, F.; Källberg, A.; Kester, O.; Litvinov, Y.; Steck, M.; Reistad, D.; Simonsson, A.; Skeppstedt, Ö.; Stöhlker, T.; Vorobjev, G.; the CRYRING@ESR working Group

    2015-11-01

    The former storage ring CRYRING has been shipped from the Manne Siegbahn Laboratory in Stockholm to Darmstadt as a Swedish in-kind contribution to FAIR. At its new location downstream of ESR all ion species presently accessible in ESR can be transferred to CRYRING, in which ions with rigidities between 1.44 and 0.054 Tm can be stored. The original Swedish layout has been modified by reconfiguring the sequence of straight sections and by slightly increasing the circumference to ESR/2. Ions can be injected from ESR or from an independent 300 keV/u RFQ test injector. The instrumentation of the ring includes an RF drift tube system for acceleration and deceleration (1 T s-1, with a possibility for an upgrade to 7 T s-1), electron cooling, a free experimental section, and both fast and slow extraction of ions. We report on the present progress of this project, give a prospective timeline, and summarize the new research which will be enabled by this project. First beam for commissioning of the storage ring is expected for 2015, final bakeout to restore ultrahigh vacuum conditions in 2016 and ion beams injected through ESR in ˜2017.

  18. Comparative study of radiation damage accumulation in Cu and Fe

    NASA Astrophysics Data System (ADS)

    Caturla, M. J.; Soneda, N.; Alonso, E.; Wirth, B. D.; Díaz de la Rubia, T.; Perlado, J. M.

    2000-01-01

    Bcc and fcc metals exhibit significant differences in behavior when exposed to neutron or heavy ion irradiation. Transmission electron microscopy (TEM) observations reveal that damage in the form of stacking fault tetrahedra (SFT) is visible in copper irradiated to very low doses, but that no damage is visible in iron irradiated to the same total dose. In order to understand and quantify this difference in behavior, we have simulated damage production and accumulation in fcc Cu and bcc Fe. We use 20 keV primary knock-on atoms (PKAs) at a homologous temperature of 0.25 of the melting point. The primary damage state was calculated using molecular dynamics (MD) with empirical, embedded-atom interatomic potentials. Damage accumulation was modeled using a kinetic Monte Carlo (kMC) algorithm to follow the evolution of all defects produced in the cascades. The diffusivities and binding energies of defects are input data for this simulation and were either extracted from experiments, the literature, or calculated using MD. MD simulations reveal that vacancy clusters are produced within the cascade core in the case of copper. In iron, most of the vacancies do not cluster during cooling of the cascade core and are available for diffusion. In addition, self-interstitial atom (SIA) clusters are produced in copper cascades but those observed in iron are smaller in number and size. The combined MD/kMC simulations reveal that the visible cluster densities obtained as a function of dose are at least one order of magnitude lower in Fe than in Cu. We compare the results with experimental measurements of cluster density and find excellent agreement between the simulations and experiments when small interstitial clusters are considered to be mobile as suggested by recent MD simulations.

  19. ESR1 mutations affect anti-proliferative responses to tamoxifen through enhanced cross-talk with IGF signaling.

    PubMed

    Gelsomino, Luca; Gu, Guowei; Rechoum, Yassine; Beyer, Amanda R; Pejerrey, Sasha M; Tsimelzon, Anna; Wang, Tao; Huffman, Kenneth; Ludlow, Andrew; Andò, Sebastiano; Fuqua, Suzanne A W

    2016-06-01

    The purpose of this study was to address the role of ESR1 hormone-binding mutations in breast cancer. Soft agar anchorage-independent growth assay, Western blot, ERE reporter transactivation assay, proximity ligation assay (PLA), coimmunoprecipitation assay, silencing assay, digital droplet PCR (ddPCR), Kaplan-Meier analysis, and statistical analysis. It is now generally accepted that estrogen receptor (ESR1) mutations occur frequently in metastatic breast cancers; however, we do not yet know how to best treat these patients. We have modeled the three most frequent hormone-binding ESR1 (HBD-ESR1) mutations (Y537N, Y537S, and D538G) using stable lentiviral transduction in human breast cancer cell lines. Effects on growth were examined in response to hormonal and targeted agents, and mutation-specific changes were studied using microarray and Western blot analysis. We determined that the HBD-ESR1 mutations alter anti-proliferative effects to tamoxifen (Tam), due to cell-intrinsic changes in activation of the insulin-like growth factor receptor (IGF1R) signaling pathway and levels of PIK3R1/PIK3R3. The selective estrogen receptor degrader, fulvestrant, significantly reduced the anchorage-independent growth of ESR1 mutant-expressing cells, while combination treatments with the mTOR inhibitor everolimus, or an inhibitor blocking IGF1R, and the insulin receptor significantly enhanced anti-proliferative responses. Using digital drop (dd) PCR, we identified mutations at high frequencies ranging from 12 % for Y537N, 5 % for Y537S, and 2 % for D538G in archived primary breast tumors from women treated with adjuvant mono-tamoxifen therapy. The HBD-ESR1 mutations were not associated with recurrence-free or overall survival in response in this patient cohort and suggest that knowledge of other cell-intrinsic factors in combination with ESR1 mutation status will be needed determine anti-proliferative responses to Tam. PMID:27178332

  20. Analysis of parameters that influence the amplitude of the ESR/alanine signal after irradiation.

    PubMed

    Dolo, J M; Feaugas, V

    2005-02-01

    When ESR/alanine dosimetry is used for comparison, the time elapsed between irradiation and measurement is critical. Several publications have already mentioned the need for monitoring some of the parameters before, during and after irradiation for accurate normalization of ESR measurements. Nevertheless, neither classification nor coupling effects have yet been mentioned. By application of an experimental design approach, some parameters such as temperature and humidity during storage, before and after irradiation, have been studied. Results are given about the way the signal tends to evolve, ranking the parameters according to their influence and the effects of parameter coupling. A comparison with a conventional approach (study of one parameter at a time) is made. It is proposed to use a normalized ESR measurement that better accounts for the chemical aspect. A better fit of the results (amplitude versus time) is observed when amplitude is corrected taking into account the water content of the dosimeter for a given relative humidity of the surrounding atmosphere during storage. PMID:15607461

  1. Wetting and spontaneous infiltration: the case study of TaC/(Au, Al and Cu) compared to TiC/Cu

    NASA Astrophysics Data System (ADS)

    Aizenshtein, M.; Froumin, N.; Nafman, O.; Frage, N.

    2016-06-01

    Spontaneous infiltration of molten metals in to ceramic skeletons, in the course MMCs' production, is related to improved wetting of the ceramic by metals. TiC is considered a "metal-like" carbide and is supposed to be wetted well by metals through metallic bonding mechanism. Nevertheless, TiC/Cu exhibit an unusual behavior since spontaneous infiltration of molten Cu takes place, while TiC is partially wetted by Cu (θ=90°).In this work we studied the relation between wetting and spontaneous infiltration in the TaC/Au, Al and Cu systems. TaC is also considered a "metal-like" carbide and indeed no chemical interaction was observed at the interfaces of the studied systems.Sessile drop experiments showed almost perfect wetting in the three system but spontaneous infiltration occurred only in the first two (e.g. TaC/Au or Al). Thermodynamic calculation shows the difference between the systems which also has its' influence on the mechanical properties of the MMCs'. Further calculation clarifies the difference between TaC/Cu and TiC/Cu infiltration behavior, but is unable to explain the wetting results differences.Correlation between wetting and spontaneous infiltration in some cases is not straight forward and more studies and calculations on the atomistic level should be done in order to clarify this matter.

  2. ESR dosimetry of fossil enamel: some comments about measurement precision, long-term signal fading and dose-response curve fitting.

    PubMed

    Duval, M; Guilarte Moreno, V; Grün, R

    2013-12-01

    This work deals with the specific studies of three main sources of uncertainty in electron spin resonance (ESR) dosimetry/dating of fossil tooth enamel: (1) the precision of the ESR measurements, (2) the long-term signal fading the selection of the fitting function. They show a different influence on the equivalent dose (D(E)) estimates. Repeated ESR measurements were performed on 17 different samples: results show a mean coefficient of variation of the ESR intensities of 1.20 ± 0.23 %, inducing a mean relative variability of 3.05 ± 2.29 % in the D(E) values. ESR signal fading over 5 y was also observed: its magnitude seems to be quite sample dependant but is nevertheless especially important for the most irradiated aliquots. This fading has an apparent random effect on the D(E) estimates. Finally, the authors provide new insights and recommendations about the fitting of ESR dose-response curves of fossil enamel with a double saturating exponential (DSE) function. The potential of a new variation of the DSE was also explored. Results of this study also show that the choice of the fitting function is of major importance, maybe more than the other sources previously mentioned, in order to get accurate final D(E) values. PMID:23832975

  3. Computational and ESR studies of electron attachment to decafluorocyclopentane, octafluorocyclobutane, and hexafluorocyclopropane: electron affinities of the molecules and the structures of their stable negative ions as determined from 13C and 19F hyperfine coupling constants.

    PubMed

    ElSohly, Adel M; Tschumper, Gregory S; Crocombe, Richard A; Wang, Jih Tzong; Williams, Ffrancon

    2005-08-01

    High-resolution ESR spectra of the ground-state negative ions of hexafluorocyclopropane (c-C3F6*-), octafluorocyclobutane (c-C4F8*-), and decafluorocyclopentane (c-C5F10*-) are reported and their isotropic 19F hyperfine coupling constants (hfcc) of 198.6 +/- 0.4 G, 147.6 +/- 0.4 G, and 117.9 +/- 0.4 G, respectively, are in inverse ratio to the total number of fluorine atoms per anion. Together with the small value of 5.2 +/- 0.4 G determined for the isotropic 13C hfcc of c-C4F8*-, these results indicate that in each case the singly occupied molecular orbital (SOMO) is delocalized over the equivalent fluorines and possesses a nodal plane through the carbon atoms of a time-averaged D(nh) structure. A series of quantum chemical computations were carried out to further characterize these anions and their neutral counterparts. Both the B3LYP density functional and second-order Møller-Plesset perturbation theory (MP2) indicate that c-C3F6*- adopts a D(3h) geometry and a (2)A2'' ground electronic state, that c-C4F8*- adopts a D(4h) geometry and a (2)A2u ground electronic state, and that c-C5F10*- adopts a C(s) structure and a (2)A' electronic state. Moreover, the 19F hyperfine coupling constants computed with the MP2 method and a high quality triple-zeta basis set are within 1% of the experimental values. Also, the values computed for the 13C hfcc of c-C4F8*- are consistent with the experimental value of 5.2 G. Therefore, in keeping with the ESR results, these negative ions derived from first-row elements can be characterized as pi* species. In addition, the hypervalency of these perfluorocycloalkane radical anions has been clarified. PMID:16045345

  4. Adsorption studies of Cu(II) on Boston fern (Nephrolepis exaltata Schott cv. Bostoniensis) leaves

    NASA Astrophysics Data System (ADS)

    Rao, Rifaqat Ali Khan; Khan, Umra

    2016-02-01

    Adsorption studies were done on Boston fern leaves for the effective removal of Cu(II) ions from aqueous solution. It has been tested for the first time for heavy metal adsorption from aqueous solution. This promising material has shown remarkable adsorption capacity towards Cu(II) ions which confirm its novelty, ease of availability, non-toxic nature, cheapness, etc., and give the main innovation to the present study. The adsorbent was analyzed by FT-IR, SEM and EDS. The effect of pH, contact time, initial metal ion concentration and temperature on the adsorption was investigated using batch process to optimize conditions for maximum adsorption. The adsorption of Cu(II) was maximum (96 %) at pH 4. The experimental data were analyzed by Langmuir, Freundlich and Tempkin isotherms. The kinetic studies of Cu(II)were carried out at room temperature (30 °C) in the concentration range 10-100 mg L-1. The data obtained fitted well with the Langmuir isotherm and pseudo-second-order kinetics model. The maximum adsorption capacity (q m) obtained from Langmuir adsorption isotherm was found to be 27.027 mg g-1 at 30 °C. The process was found to be exothermic and spontaneous in nature. The breakthrough and exhaustive capacities were found to be 12.5 and 37.5 mg g-1, respectively. Desorption studies showed that 93.3 % Cu(II) could be desorbed with 0.1 M HCl by continuous mode.

  5. Synthesis, Characterization, and Cu(2+) Coordination Studies of a 3-Hydroxy-4-pyridinone Aza Scorpiand Derivative.

    PubMed

    López-Martínez, Luis M; Pitarch-Jarque, Javier; Martínez-Camarena, Àlvar; García-España, Enrique; Tejero, Roberto; Santacruz-Ortega, Hisila; Navarro, Rosa-Elena; Sotelo-Mundo, Rogerio R; Leyva-Peralta, Mario Alberto; Doménech-Carbó, Antonio; Verdejo, Begoña

    2016-08-01

    The synthesis, acid-base behavior, and Cu(2+) coordination chemistry of a new ligand (L1) consisting of an azamacrocyclic core appended with a lateral chain containing a 3-hydroxy-2-methyl-4(1H)-pyridinone group have been studied by potentiometry, cyclic voltammetry, and NMR and UV-vis spectroscopy. UV-vis and NMR studies showed that phenolate group was protonated at the highest pH values [log K = 9.72(1)]. Potentiometric studies point out the formation of Cu(2+) complexes of 1:2, 2:2, 4:3, 1:1, and 2:1 Cu(2+)/L1 stoichiometries. UV-vis analysis and electrochemical studies evidence the implication of the pyridinone moieties in the metal coordination of the 1:2 Cu(2+)/L1 complexes. L1 shows a stronger chelating ability than the reference chelating ligand deferiprone. While L1 shows no cytotoxicity in HeLa and ARPE-19 human cell lines (3.1-25.0 μg/mL), it has significant antioxidant activity, as denoted by TEAC assays at physiological pH. The addition of Cu(2+) diminishes the antioxidant activity because of its coordination to the pyridinone moiety phenolic group. PMID:27433814

  6. Cu-Au, Ag-Au, Cu-Ag, and Ni-Au intermetallics: First-principles study of temperature-composition phase diagrams and structures

    NASA Astrophysics Data System (ADS)

    Ozoliņš, V.; Wolverton, C.; Zunger, Alex

    1998-03-01

    The classic metallurgical systems-noble-metal alloys-that have formed the benchmark for various alloy theories are revisited. First-principles fully relaxed general-potential linearized augmented plane-wave (LAPW) total energies of a few ordered structures are used as input to a mixed-space cluster expansion calculation to study the phase stability, thermodynamic properties, and bond lengths in Cu-Au, Ag-Au, Cu-Ag, and Ni-Au alloys. (i) Our theoretical calculations correctly reproduce the tendencies of Ag-Au and Cu-Au to form compounds and Ni-Au and Cu-Ag to phase separate at T=0 K. (ii) Of all possible structures, Cu3Au (L12) and CuAu (L10) are found to be the most stable low-temperature phases of Cu1-xAux with transition temperatures of 530 K and 660 K, respectively, compared to the experimental values 663 K and ~670 K. The significant improvement over previous first-principles studies is attributed to the more accurate treatment of atomic relaxations in the present work. (iii) LAPW formation enthalpies demonstrate that L12, the commonly assumed stable phase of CuAu3, is not the ground state for Au-rich alloys, but rather that ordered (100) superlattices are stabilized. (iv) We extract the nonconfigurational (e.g., vibrational) entropies of formation and obtain large values for the size-mismatched systems: 0.48 kB/atom in Ni0.5Au0.5 (T=1100 K), 0.37 kB/atom in Cu0.141Ag0.859 (T=1052 K), and 0.16 kB/atom in Cu0.5Au0.5 (T=800 K). (v) Using 8 atom/cell special quasirandom structures we study the bond lengths in disordered Cu-Au and Ni-Au alloys and obtain good qualitative agreement with recent extended x-ray-absorption fine-structure measurements.

  7. Anisotropy of Multilayered (cu, C)BA2CA3CU4OY Superconductors Studied by Torque Magnetometry

    NASA Astrophysics Data System (ADS)

    Tokiwa, K.; Koganezawa, T.; Mikusu, S.; Watanabe, T.; Iyo, A.; Tanaka, Y.

    The magnetic torque of (Cu,C)Ba2Ca3Cu4Oy ( (Cu,C)-1234) aligned samples with various carrier concentrations has been measured under a magnetic field of 9 T at 80 K and 90 K. The carrier concentration was determined by Hall effect measurements. From angular dependent torque measurements, the anisotropy ratio γ was estimated using the 3D anisotropic London model. The γvalues decreased from 23 to 10 with an increase in the average Hall number per CuO2 plane (nH); however, these samples showed a nearly constant Tc of about 117 K. These results indicate that the anisotropy of (Cu,C)-1234 strongly reflects the doping levels of the outer planes.

  8. The Association between ESR and CRP and Systemic Hypertension in Sarcoidosis.

    PubMed

    Mirsaeidi, Mehdi; Omar, Hesham R; Ebrahimi, Golnaz; Campos, Micheal

    2016-01-01

    Introduction. The association between the level of systemic inflammation and systemic hypertension (sHTN) among subjects with sarcoidosis has not been previously explored. Methods. A retrospective study was conducted to investigate the relation between the level of systemic inflammation in sarcoidosis, measured by various serum inflammatory markers, and sHTN. Results. Among a total of 108 cases with sarcoidosis (mean age: 53.4 years, 76.9% females), 55 (50.9%) had sHTN and 53 (49.1%) were normotensive. ESR was highly associated with sHTN. The patients with sHTN had higher mean ESR levels compared with normotensives (48.8 ± 35 versus 23.2 ± 27 mm/hr, resp.; P = 0.001). ROC curve analysis for ESR revealed an AUC value of 0.795 (95% CI: 0.692-0.897; P = 0.0001). With regard to CRP, there was a trend towards higher mean values in sHTN group (3.4 versus 1.7 mg/L; P = 0.067) and significantly higher prevalence of sHTN in the highest CRP quartile compared to the lowest one (69.6% versus 30%; OR 4.95; P = 0.017). ROC curve analysis for CRP revealed an AUC value of 0.644 (95% CI: 0.518-0.769; P = 0.03). On multivariate analysis, ESR and the CRP remained independent predictors for sHTN among subjects with sarcoidosis. Conclusion. Systemic inflammation is associated with the presence of sHTN in sarcoidosis. PMID:27433355

  9. The Association between ESR and CRP and Systemic Hypertension in Sarcoidosis

    PubMed Central

    Mirsaeidi, Mehdi; Omar, Hesham R.; Ebrahimi, Golnaz; Campos, Micheal

    2016-01-01

    Introduction. The association between the level of systemic inflammation and systemic hypertension (sHTN) among subjects with sarcoidosis has not been previously explored. Methods. A retrospective study was conducted to investigate the relation between the level of systemic inflammation in sarcoidosis, measured by various serum inflammatory markers, and sHTN. Results. Among a total of 108 cases with sarcoidosis (mean age: 53.4 years, 76.9% females), 55 (50.9%) had sHTN and 53 (49.1%) were normotensive. ESR was highly associated with sHTN. The patients with sHTN had higher mean ESR levels compared with normotensives (48.8 ± 35 versus 23.2 ± 27 mm/hr, resp.; P = 0.001). ROC curve analysis for ESR revealed an AUC value of 0.795 (95% CI: 0.692–0.897; P = 0.0001). With regard to CRP, there was a trend towards higher mean values in sHTN group (3.4 versus 1.7 mg/L; P = 0.067) and significantly higher prevalence of sHTN in the highest CRP quartile compared to the lowest one (69.6% versus 30%; OR 4.95; P = 0.017). ROC curve analysis for CRP revealed an AUC value of 0.644 (95% CI: 0.518–0.769; P = 0.03). On multivariate analysis, ESR and the CRP remained independent predictors for sHTN among subjects with sarcoidosis. Conclusion. Systemic inflammation is associated with the presence of sHTN in sarcoidosis. PMID:27433355

  10. First-principles study on electronic structure and optical properties of Cu-doped β-Ga2O3

    NASA Astrophysics Data System (ADS)

    Yan, Huiyu; Guo, Yanrui; Song, Qinggong; Chen, Yifei

    2014-02-01

    The electronic and optical properties of the Cu-doped and intrinsic β-Ga2O3 are studied by using the first-principles calculation method. Results show that Cu-doped β-Ga2O3 can be fabricated in experiments. Two acceptor impurity levels are introduced near the top of the valence band by Cu dopant, indicating that Cu-doped gallium oxide is a promising p-type semiconductor. Cu-doped β-Ga2O3 can be used as intermediate band semiconductor in solar cell. Cu dopant induced 100% spin polarization near the Fermi level. The analysis results of optical properties reveal that Cu-doped β-Ga2O3 is a promising potential candidate for p-type ultraviolet (UV) transparent semiconductor.

  11. Computer enhancement of ESR spectra of magnetite nanoparticles

    NASA Astrophysics Data System (ADS)

    Dobosz, B.; Krzyminiewski, R.; Koralewski, M.; Hałupka-Bryl, M.

    2016-06-01

    We present ESR measurements of non-interacting magnetic nanoparticle systems. Temperature and orientational dependence of ESR spectra were measured for Fe3O4 nanoparticle coated by dextran or oleic acid, frozen in different magnetic field. Several parameters describing magnetic properties such as g-factor, line width, the anisotropy constant were calculated and discussed. The ESR spectra of investigated nanoparticles were also subjected to Computer Resolution Enhancement Method (CREM). This procedure allows to separate a narrow line on the background of the broad line, which presence in this type of materials was recognized in the recent literature and have been further discussed in the paper. CREM is a valuable tool for monitoring of changes on the surface of magnetic core of nanoparticles.

  12. Djurleite (Cu1.94S) and low chalcocite (Cu2S): New crystal structure studies

    USGS Publications Warehouse

    Evans, H.T., Jr.

    1979-01-01

    Additional x-ray structure studies on low chalcocite generally confirm the previously reported structure but show that either disorder is present or the true space group is not P21/c but Pc, four of the 96 copper atoms in the monoclinic unit cell taking on twofold (linear) coordination. The crystal structure of djurleite has been solved in space group P21/n, the monoclinic cell having parameters a = 26.897, b = 15.745, and c = 13.565 angstroms; ?? = 90.13??; and a content of 248 copper and 128 sulfur atoms. Of the 62 different copper atoms in the structure, 52 are in threefold, triangular coordination with sulfur, nine in tetrahedral, and one in linear coordination.

  13. Dielectric resonator-based resonant structure for sensitive ESR measurements at high-hydrostatic pressures.

    PubMed

    Sienkiewicz, Andrzej; Vileno, Bertrand; Garaj, Slaven; Jaworski, Marek; Forró, László

    2005-12-01

    We present a newly developed microwave probe head that accommodates a gasketed sapphire anvil cell (SAC) for performing sensitive electron spin resonance (ESR) measurements under high-hydrostatic pressures. The system was designed around commercially available dielectric resonators (DRs) having the dielectric permittivity of approximately 30. The microwave resonant structure operates in a wide-stretched double-stacked geometry and resonates in the lowest cylindrical quasi TE(011) mode around 9.2 GHz. The most vital parts of the probe's microwave heart were made of plastic materials, thus making the resonant structure transparent to magnetic field modulation at 100 kHz. The overall ESR sensitivity of the probe was demonstrated for a small speck of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) positioned in the gasket of the SAC, using water as the pressure-transmitting medium. The system was also used for studying pressure-induced changes in spin-relaxation mechanisms of a quasi-1D-conducting polymer, K(1)C(60). For small samples located in the sample hole of the gasket the probe reveals sensitivity that is only approximately 3 times less than that yielded by regular ESR cavities. PMID:16168687

  14. Influence of A-site substitution on ESR spectra of lanthanum manganite perovskites

    NASA Astrophysics Data System (ADS)

    Phan, T. L.; Tho, N. D.; Bau, L. V.; Phuc, N. X.; Yu, S. C.

    2006-08-01

    We studied electron spin resonance (ESR) spectra of La 0.7A' 0.3MnO 3 (A'=Sr, Ba, Pb, and Cd) perovskites in a large range of temperature, from their Curie temperature to ˜500 K. Asymmetrical EPR signals at temperatures TESR linewidth. The ESR linewidth vs. temperature, Δ H( T), in the region T>Tmin well fits to the model of adiabatic hopping motion of small polarons ΔH(T)=ΔH0+(a/T) exp(-E/kT), where Ea and kB are the activation energy and the Boltzmann factor, respectively; Δ H0 and a are constants. It is worth noticing that, in this temperature range, the Lande factor g for the samples is about 2.00, indicating spin-spin interaction among electrons of Mn 3+ and Mn 4+ ions playing an important role.

  15. Effect of Cu2+ Activation on Interfacial Water Structure at the Sphalerite Surface as Studied by Molecular Dynamics Simulation

    SciTech Connect

    Jin, Jiaqi; Miller, Jan D.; Dang, Liem X.; Wick, Collin D.

    2015-12-10

    In the first part of this paper, an experimental contact angle study of the fresh and Cu2+ activated sphalerite-ZnS surface as well as the covellite-CuS (001) surface is reported describing the increased hydrophobic character of the surface during Cu2+ activation. In addition to these experimental results, the fresh sphalerite-ZnS (110), copper-zinc sulfide-CuZnS2 (110), villamaninite- CuS2 (100), and covellite-CuS (001) surfaces were examined using Molecular Dynamics Simulation (MDS). Our MDS results on the behavior of interfacial water at the fresh sphalerite-ZnS (110), copper-zinc sulfide-CuZnS2 (110), villamaninite-CuS2 (100), and covellite-CuS (001) surfaces include simulated contact angles, water number density distribution, water dipole orientation, water residence time, and hydrogen-bonding considerations. The copper content at the Cu2+ activated sphalerite surface seems to account for the increased hydrophobicity as revealed by both experimental and MD simulated contact angle measurements. The relatively greater hydrophobic character developed at the Cu2+ activated sphalerite surface and at the copper-zinc sulfide surface has been described by MDS, based on the structure of interfacial water and its dynamic properties. L.X.D. acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  16. A theoretical study of surface-structural sensitivity of the reverse water-gas shift reaction over Cu( hkl) surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Gui-Chang; Jiang, Ling; Pang, Xian-Yong; Cai, Zun-Sheng; Pan, Yin-Ming; Zhao, Xue-Zhuang; Morikawa, Yoshitada; Nakamura, Junji

    2003-10-01

    The surface-structural sensitivity of the reverse water-gas shift (RWGS) reaction (CO 2 + H 2 → CO + H 2O) over the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces has been studied by first-principle density functional calculations together with the UBI-QEP approach. Cluster models of the surface have been employed to simulate the adsorption of CO 2, H 2, H, O, OH, CO, and H 2O on the Cu( hkl) surfaces at low coverage. This sensitivity is determined by the difference in the activation barriers. It can be noticed that the most likely rate-determining step in RWGS reaction is the CO 2 dissociative adsorption, namely CO 2,g → CO s + O s. The trend in the calculated activation barriers for the reaction of CO 2 dissociative adsorption follows the order of Cu(1 1 0) < Cu(1 0 0) < Cu(1 1 1), suggesting that the most efficient crystal surface for catalyzing RWGS reaction by copper is Cu(1 1 0), and the more densely packed Cu(1 1 1) surface is the least active among the Cu( hkl) surfaces studied here. As expected, the activation barriers for the recombinative reactions over Cu( hkl) are in the order of Cu(1 1 0) > Cu(1 0 0) > Cu(1 1 1), just opposite to the dissociative reactions. The interesting thing is that there is a good correlation between the adsorption bond length and the adsorption energy: The preferred adsorption site is the one with the shortest adsorption bond length. The present calculations are in good agreement with experimental observations.

  17. Combined ESR and thermodynamic studies of the superoxide adduct of 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide (DEPMPO): hindered rotation around the O-O bond evidenced by two-dimensional simulation of temperature-dependent spectra.

    PubMed

    Rockenbauer, Antal; Clément, Jean-Louis; Culcasi, Marcel; Mercier, Anne; Tordo, Paul; Pietri, Sylvia

    2007-06-14

    Experiments were performed to elucidate the origin of the superhyperfine structure and line width alternation (LWA) seen in the ESR spectrum of the major diastereoisomer (1) of DEPMPO-OOH, the remarkably persistent superoxide adduct of 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide (DEPMPO). Using selectively deuterated DEPMPO derivatives, we demonstrated that the superhyperfine pattern can be unambiguously attributed to long-range couplings. The recording in pyridine of highly resolved spectra in a wide temperature range, combined with two-dimensional simulation, allowed us to characterize an inverted LWA in 1 and revealed a uniform line broadening in the spectrum of the minor DEPMPO-OOH diastereoisomer (2), with both effects originating from a chemical exchange between conformers. When the individual spectra of 1 presenting LWA in the fast-exchange regime were simulated, four equally good fits were obtained and this ambiguity could be resolved by using a two-dimensional simulation technique. The thermodynamic and kinetic constants of this exchange were consistent with a rotation around the O-O bond. We propose that line broadening effects in 1 and 2 result from this O-O rotation concerted with the pseudo-rotation of the pyrrolidine ring. PMID:17518450

  18. Nitrogen addition using a gas blow in an ESR process

    NASA Astrophysics Data System (ADS)

    Yamamoto, S.; Momoi, Y.; Kajikawa, K.

    2016-07-01

    A new nitrogen method for adding in an ESR process using nitrogen gas blown in through the electrode was investigated. Nitrogen gas blown through a center bore of the electrode enabled contact between the nitrogen gas and the molten steel directly underneath the electrode tip. A ɸ 145mm diameter, laboratory-sized PESR furnace was used for the study on the reaction kinetics. Also, we carried out a water-model experiment in order to check the injection depth of the gas blown in the slag. The water model showed that the gas did not reach the upper surface of the molten metal and flowed on the bottom surface of the electrode only. An EPMA was carried out for a droplet remaining on the tip of the electrode after melting. The molten steel from the tip of the electrode shows that nitrogen gas absorption occurred at the tip of the electrode. The mass transfer coefficient was around 1.0x10-2 cm/sec in the system. This value is almost the same as the coefficient at the molten steel free surface.

  19. Fe-57 and Sn-119 Moessbauer study of La2CuO(4-y), YBa2Cu3O(7-y) and SmBa2Cu3O(7-y)

    NASA Technical Reports Server (NTRS)

    Jha, S.; Mitros, C.; Yehia, S.; Lahamer, Amer; Julian, Glenn M.

    1988-01-01

    Moessbauer studies reveal antiferromagnetic order in doped La2CuO(4-7): at 77 K, H = 476 kOe at Fe-57 and H is less that 10 kOe at Sn-119. Split-source and conventional absorber experiments on RBa2Cu3O(7-y) (R = Y, Sm) are consistent with occupation of 3 sites by Fe-57, the relative population depending on sample preparation and Fe concentration.

  20. Superconducting microstrip resonator for pulsed ESR of thin films.

    PubMed

    Benningshof, O W B; Mohebbi, H R; Taminiau, I A J; Miao, G X; Cory, D G

    2013-05-01

    This article describes a superconducting microstrip resonator operating at 9.5 GHz (X-band) that is specially designed for pulsed ESR on thin films. A novel configuration consisting of an array of half-wave length microstrip transmission lines generates a uniform magnetic field over a 2-D region of 100×1000 μm(2) with field homogeneity better than 5×10(-2). Using the device, we demonstrate strong coupling of the resonator to an electron spin ensemble and pulsed ESR on Si:P. PMID:23454577

  1. Local structure analysis of some Cu(II) theophylline complexes

    NASA Astrophysics Data System (ADS)

    David, L.; Cozar, O.; Forizs, E.; Cr ăciun, C.; Ristoiu, D.; B ălan, C.

    1999-10-01

    The CuT 2L 2·2H 2O complexes [T=Theophylline (1,3-dimethylxanthine); L=NH 3, n-propylamine (npa), 2-aminoethanol (ae)] were prepared and investigated by ESR spectroscopy. Powder ESR spectrum of CuT 2(NH 3) 2·2H 2O is axial ( g||=2.255, g⊥=2.059). ESR spectrum of CuT 2(npa) 2·2H 2O with ( g||=2.299, g⊥=2.081) is a superposition of one axial ( g||=2.299, g⊥=2.073) and one isotropic component ( g0≈2.089), in the same amount. The axial spectra of the former complexes are due to a static Jahn-Teller effect ( EJT≈2880 cm -1). ESR spectrum of CuT 2(ae) 2·2H 2O is orthorhombic ( g1c=2.199, g2c=2.095, g3c=2.037). The local symmetries around the Cu(II) ions remain unchanged by DMF solvating, by adsorbing these solutions on NaY zeolite or by lowering the temperature.

  2. Free and Cued Selective Reminding Test: an Italian normative study.

    PubMed

    Frasson, P; Ghiretti, R; Catricalà, E; Pomati, S; Marcone, A; Parisi, L; Rossini, P M; Cappa, S F; Mariani, C; Vanacore, N; Clerici, F

    2011-12-01

    The presence of episodic memory impairment is required for the diagnosis of Alzheimer's dementia by all current diagnostic criteria. The new research criteria proposed by Dubois et al. (Lancet Neurol 6:734-746, 2007) require that the impairment should not improve significantly with cueing, recognition testing nor after the control of effective encoding. This is considered to be the core deficit of "prodromal Alzheimer's disease". The Free and Cued Selective Reminding Test (FCSRT) is a memory test that allows in assessing these specific features of memory impairment. Here, we report normative data for an Italian version of the FCSRT. The test is based on the 12 pictorial stimuli, 6 belonging to the living domain, and 6 to the non-living domain. Six scores were derived from the performance of 227 healthy Italian adults, with age, sex and education homogenously distributed across subgroups: immediate free recall (IFR), immediate total recall (ITR), delayed-free recall (DFR), delayed total recall (DTR), Index of Sensitivity of Cueing (ISC), number of intrusions. In multiple regression analyses, age emerged as an influencing factor for both IFR and DFR, with older people obtaining lower scores. Education and gender appear to influence only IFR, with better performance by more educated subjects and females. Adjusted scores were used to determine inferential cutoff scores and to compute equivalent scores. PMID:21594655

  3. First-principles Study of Lattice Thermal Conductivity of Cu3SbS4andCu3SbSe4

    NASA Astrophysics Data System (ADS)

    Xia, Yi; Zhou, Fei; Nielson, Weston; Ozolins, Vidvuds

    2015-03-01

    Linearized self-consistent Boltzmann transport equation (BTE), utilizing interatomic force constants (IFCs) obtained via compressive sensing lattice dynamics (CSLD), is used to study the lattice thermal conductivity (κl) of Cu3SbS4, Cu3SbSe4 and their solid solutions. With these IFCs we obtain bulk lattice thermal conductivity in good agreement with experimental measurements. We also compare Cu3SbS4andCu3SbSe4 with respect to Grüneisen parameter, group velocity, phonon lifetime, mean free path and cumulative κl. All the analysis indicates that (1) slightly larger group velocity and lifetime of acoustic modes found in Cu3SbS4 lead to larger κl compared with Cu3SbSe4 over the whole temperature range. Contributions from optical modes to κl for both compounds are about 25% at temperature higher than 300K. This large portion of κl can not be neglected if one aims to predict accurate κl; (2) Nanostructures with length less than 10nm can effectively reduce κl by about 80% for both of the compounds; (3) solid solution of two compounds can effectively reduce κl as much as 40% at room temperature.

  4. Comparative Study of Cu Films Prepared by DC, High-Power Pulsed and Burst Magnetron Sputtering

    NASA Astrophysics Data System (ADS)

    Solovyev, A. A.; Oskirko, V. O.; Semenov, V. A.; Oskomov, K. V.; Rabotkin, S. V.

    2016-05-01

    A comparative study of deposition rate, adhesion, structural and electrical properties of nanocrystalline copper thin films deposited using direct current magnetron sputtering (DCMS) and different regimes of high power pulsed magnetron sputtering is presented. High-power impulse magnetron sputtering (HIPIMS) and burst regime (pulse packages) of magnetron sputtering are investigated. The ion and atomic flows toward the growing film during magnetron sputtering of a Cu target are determined. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used to observe the structural characterization of the films. The resistivity of the films was measured using four-point probe technique. In all sputtering regimes, Cu films have mixture crystalline orientations of [111], [200], [311] and [220] in the direction of the film growth. As peak power density in studied deposition regimes was different in order of magnitude (from 15 W/cm2 in DC regime to 3700 W/cm2 in HIPIMS), film properties were also greatly different. DCMS Cu films exhibit a porous columnar grain structure. In contrast, HIPIMS Cu films have a slightly columnar and denser composition. Cu films deposited using burst regimes at peak power density of 415 W cm-2 and ion-to-atom ratio of about 5 have the densest composition and smallest electrical resistance.

  5. Comparative Study of Cu Films Prepared by DC, High-Power Pulsed and Burst Magnetron Sputtering

    NASA Astrophysics Data System (ADS)

    Solovyev, A. A.; Oskirko, V. O.; Semenov, V. A.; Oskomov, K. V.; Rabotkin, S. V.

    2016-08-01

    A comparative study of deposition rate, adhesion, structural and electrical properties of nanocrystalline copper thin films deposited using direct current magnetron sputtering (DCMS) and different regimes of high power pulsed magnetron sputtering is presented. High-power impulse magnetron sputtering (HIPIMS) and burst regime (pulse packages) of magnetron sputtering are investigated. The ion and atomic flows toward the growing film during magnetron sputtering of a Cu target are determined. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used to observe the structural characterization of the films. The resistivity of the films was measured using four-point probe technique. In all sputtering regimes, Cu films have mixture crystalline orientations of [111], [200], [311] and [220] in the direction of the film growth. As peak power density in studied deposition regimes was different in order of magnitude (from 15 W/cm2 in DC regime to 3700 W/cm2 in HIPIMS), film properties were also greatly different. DCMS Cu films exhibit a porous columnar grain structure. In contrast, HIPIMS Cu films have a slightly columnar and denser composition. Cu films deposited using burst regimes at peak power density of 415 W cm-2 and ion-to-atom ratio of about 5 have the densest composition and smallest electrical resistance.

  6. Contribution of polymorphisms in ESR1, ESR2, FSHR, CYP19A1, SHBG, and NRIP1 genes to migraine susceptibility in Turkish population.

    PubMed

    CoŞkun, Salih; Yůcel, Yavuz; Çim, Abdullah; Cengiz, Beyhan; Oztuzcu, Serdar; Varol, Sefer; Özdemir, Hasan H; Uzar, ErtuĞrul

    2016-03-01

    Migraine, a highly prevalent headache disorder, is regarded as a polygenic multifactorial disease. Single-nucleotide polymorphisms (SNPs) in the genes that involved in sex hormone metabolism may comprise risk for migraine, but the results of previous genetic association studies are conflicting. The aim of this study was to evaluate genetic variants in genes involved in oestrogen receptor and oestrogen hormone metabolism in a Turkish population. A total of 12 SNPs in the ESR1, ESR2, FSHR, CYP19A1, SHBG and NRIP1 genes were genotyped in 142 migraine cases and 141 nonmigraine controls, using a BioMark 96.96 dynamic array system. In addition, gene-gene interactions were analysed using generalized multifactor dimensionality reduction (GMDR) methods. According to GMDR analysis, our results indicated that there was a significant association between migraine and gene-gene interaction among the CYP19A1, FSHR, ESR1 and NRIP1. Single-gene variant analysis showed that a significant association was observed between the TT genotype of rs10046 and migraine susceptibility.When the analysis was performed only in women, the GG genotype of rs2229741 was different between migraineurs and controls.When the female migraine patients were divided into two groups, migraine related to menstruation (MRM) or migraine not related to menstruation (MNRM), GG genotype of rs726281 was significantly associated with MRM. These results suggested that rs10046 could play a potential role in migraine susceptibility in Turkish population. Also, the rare GG genotype of rs726281 appears to influence migraine susceptibility in a recessive manner in MRM subgroup of female patients. In addition, variant GG genotype of rs2229741 may reduce the risk of migraine in Turkish women. PMID:27019440

  7. NQR-NMR studies of higher alcohol synthesis Cu-Co catalysts

    SciTech Connect

    Not Available

    1991-12-17

    Our previous studies (1,2) on the zerofield NMR spectra of Cu/Co catalysts revealed that the method of preparation sensitively influences the magnetic character of the Catalyst. Catalytic studies of the earlier investigators also (3) show similar influence on the product selectivity and indicate reproducible performance is critically dependent on the control and rigor of the preparation technique. To compliment the NMR results, we have made a thorough investigation of the Hysteresis character of the Cu/Co catalysts with the metal ratio varying from 0.2 to 4.0.

  8. Attempt at ESR dating of tooth enamel of French middle Pleistocene sites.

    PubMed

    Bahain, J J; Sarcia, M N; Falguères, C; Yokoyama, Y

    1993-01-01

    Tooth enamel samples from four important French middle Pleistocene sites are analyzed by the ESR method. ESR ages were calculated using uranium uptake mathematical models and compared with U-series results. PMID:8386043

  9. Ab-initio study of encapsulated and functionalized silicon nanotube with a monoatomically thin Cu wire

    SciTech Connect

    Chandel, Surjeet Kumar; Ahluwalia, P. K.; Sharma, Raman; Kumar, Arun

    2015-06-24

    First principle calculations based on DFT have been performed to study the interaction of monoatomically thin Cu wire with silicon nanotube in armchair configuration having chirality (6, 6) both by placing it inside (encapsulation) and outside (functionalisation) the tube. The lowest energy for positioning monoatomically thin Cu wire inside and outside surfaces of SiNT were found to possess cohesive energies of 4.03 eV and 4.02 eV respectively and hence the stability of both SiNTs is found to be almost same. However, From the electronic band structures study, the conductance in case of SiNT for the encapsulated and functionalized positioning of the Cu wire have been found to be 2G{sub 0} and 4G{sub 0} respectively showing enhanced conductance for the functionalized SiNT.

  10. A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces

    SciTech Connect

    Liu P.; Yang, Y.; White, M.G.

    2012-01-12

    Density functional theory (DFT) calculations and Kinetic Monte Carlo (KMC) simulations were employed to investigate the methanol synthesis reaction from CO{sub 2} hydrogenation (CO{sub 2} + 3H{sub 2} {yields} CH{sub 3}OH + H{sub 2}O) on metal-doped Cu(111) surfaces. Both the formate pathway and the reverse water-gas shift (RWGS) reaction followed by a CO hydrogenation pathway (RWGS + CO-Hydro) were considered in the study. Our calculations showed that the overall methanol yield increased in the sequence: Au/Cu(111) < Cu(111) < Pd/Cu(111) < Rh/Cu(111) < Pt/Cu(111) < Ni/Cu(111). On Au/Cu(111) and Cu(111), the formate pathway dominates the methanol production. Doping Au does not help the methanol synthesis on Cu(111). Pd, Rh, Pt, and Ni are able to promote the methanol production on Cu(111), where the conversion via the RWGS + CO-Hydro pathway is much faster than that via the formate pathway. Further kinetic analysis revealed that the methanol yield on Cu(111) was controlled by three factors: the dioxomethylene hydrogenation barrier, the CO binding energy, and the CO hydrogenation barrier. Accordingly, two possible descriptors are identified which can be used to describe the catalytic activity of Cu-based catalysts toward methanol synthesis. One is the activation barrier of dioxomethylene hydrogenation, and the other is the CO binding energy. An ideal Cu-based catalyst for the methanol synthesis via CO{sub 2} hydrogenation should be able to hydrogenate dioxomethylene easily and bond CO moderately, being strong enough to favor the desired CO hydrogenation rather than CO desorption but weak enough to prevent CO poisoning. In this way, the methanol production via both the formate and the RWGS + CO-Hydro pathways can be facilitated.

  11. Estrogen Receptor Alpha (ESR1) Gene Polymorphisms in Pre-eclamptic Saudi Patients

    PubMed Central

    El-Beshbishy, Hesham A.; Tawfeek, Manal A.; Al-Azhary, Nevin M.; Mariah, Reham A.; Habib, Fawzia A.; Aljayar, Lamya; Alahmadi, Abrar F.

    2015-01-01

    Objectives: Pre-eclampsia causes maternal mortality worldwide. Estrogen receptor alpha (ESR1) gene polymorphisms were responsible for cardiovascular diseases. This case control study was conducted to investigate whether 2 polymorphic genes of ESR1 are associated with pre-eclampsia among Saudi women in Madina city, Saudi Arabia. Methods: Blood samples from 97 pre-eclamptic and 94 healthy pregnant women were analyzed using restriction fragment length polymorphism-polymerase chain reaction method. All the subjects were recruited randomly from outpatient clinics of Madina Maternity Children Hospital (MMCH), Madina, Saudi Arabia, between Dec. 2012 and Jan. 2014. Results: There was no association between pre-eclampsia and PvuII and XbaI ESR1 gene polymorphisms individually. TT/AA and TT/AG genotype combination existed significantly in pre-eclamptic patients compared to control. The frequency of PvuII and XbaI combined TT/AA genotypes between pre-eclamptic women was 36.1% vs 9.6%, however, frequency of PvuII and XbaI combined TT/AG genotypes between pre-eclamptic women was 3.1% vs 17%, compared to control. The homozygous T-A haplotype carriers showed high pre-eclampsia risk, independent of pregnancy, BMI and smoking status (adjusted odds ratio (OR): 3.26, 95% confidence interval (CI):1.71-9.21). The heterozygous T-A haplotype carriers did not differ from that of non-carriers (adjusted OR: 1.12, 95% CI: 0.47-2.75). No association was observed between pre-eclampsia and T-G, C-G and C-A haplotype of PvuII and XbaIESR1 gene polymorphisms. Conclusions: T-A haplotype of homozygous associated with pre eclampsia not heterozygous carriers of ESR 1 PvuII and XbaI gene polymorphisms elicited high risk of pre-eclampsia. GG genotype of XbaI polymorphism decreased pre-eclampsia risk. Further studies using larger sample size are recommended to investigate the ESR 1 gene polymorphisms associated with pre-eclampsia. PMID:26430422

  12. Plane wave density functional molecular dynamics study of exothermic reactions of Al/CuO thermites

    NASA Astrophysics Data System (ADS)

    Oloriegbe, Suleiman; Sewell, Thomas; Chen, Zhen; Jiang, Shan; Gan, Yong

    2014-03-01

    Exothermic reactions between nanosize aluminum (Al) and copper oxide (CuO) structures are of current interest because of their high reaction enthalpy and energy density which exceed those of traditional monomolecular energetic compounds such as TNT, RDX, and HMX. In this work, molecular dynamics simulations with forces obtained from plane wave density functional theory are used to investigate the atomic-scale and electronic processes that occur during the fast thermite reactions between Al and CuO nanostructures under adiabatic conditions. Aluminum surfaces in contact with O-exposed and Cu-exposed CuO surfaces are studied. Starting from initial temperature T = 800 K, we have observed: faster chemical reaction at the oxygen-rich interface during the initial 0.5 ps, linear temperature rise, and fast oxygen diffusion into the Al region with the rate 1.87 X 10-3 cm2/s. The density-derived electrostatic and chemical method is used to evaluate the net atomic charges and charge transfer during the important redox processes. High charge density around the oxygen-exposed interface may be responsible for the faster initial reactions at that interface. The overall reaction rate, determined using the time evolution of Cu-O charge orbital overlap population, is approximately first order.

  13. Optical chemosensors for Cu(II) ion based on BODIPY derivatives: an experimental and theoretical study.

    PubMed

    Keawwangchai, Tasawan; Wanno, Banchob; Morakot, Nongnit; Keawwangchai, Somchai

    2013-10-01

    Two BODIPY derivatives for Cu(2+) ion chemosensors containing 4-[2-(diethylamino)-2-oxoethoxy]phenyl (BDP1) and 3,4-bis[2-(diethylamino)-2-oxoethoxy]phenyl (BDP2) were synthesized by coupling appropriate N,N-diethyl-2-(4-formylphenoxy)acetamide and 2,4-dimethylpyrrole moieties in the presence of trifluoroacetic acid and anhydrous dichloromethane at room temperature. The binding abilities between these chemosensors and 50 equivalents of Na(+), K(+), Ag(+), Ca(2+), Fe(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+) ions were studied using UV-vis and fluorescence spectrophotometry. The results show that, compared to other ions, both the UV-vis absorption and fluorescence emission intensity of BDP2 decreased dramatically when Cu(2+) ion was added. To explain this behavior, ab initio quantum chemical calculations were performed using correlated second-order Møller-Plesset perturbation theory (MP2/LanL2DZ). The calculated orbital energies indicated that the decrease in UV-vis absorption intensity and the quenching of fluorescene emission were due to the single-electron reduction of Cu(2+) to Cu(+) ion. PMID:23748557

  14. Studies on the thermal stability of BiCuSeO

    SciTech Connect

    Barreteau, Celine; Berardan, David Dragoe, Nita

    2015-02-15

    BiCuSeO based materials have been reported as very promising thermoelectric materials, with thermoelectric figure of merit values that make them among the best p-type Pb-free polycrystalline thermoelectric materials, and they could be suitable for applications in thermal to electrical power conversion modules in a 300–650 °C temperature range. In this paper, we report on the phase stability and thermal stability of these materials under inert and oxidizing atmosphere and we discuss their actual potential for wide scale applications. We show that although they are stable in inert atmosphere up to 650 °C, with very slow volatilization rate, it is not the case under oxidizing atmosphere, with a quick oxidation starting at a moderate temperature. - Graphical abstract: BiCuSeO oxidation under air, starting below 300 °C. - Highlights: • Decomposition and oxidation mechanisms of BiCuSeO were studied. • BiCuSeO does not volatilize in inert atmosphere up to 650 °C. • BiCuSeO starts oxidizing for temperatures as low as 200 °C.

  15. Density functional study of CaN mono and bilayer on Cu(001)

    SciTech Connect

    Zahedifar, Maedeh; Hashemifar, S. Javad Akbarzadeh, Hadi

    2014-01-15

    Density functional - pseudopotential calculations are performed to provide first-principles insights into magnetic behaviour of bulk CaN and CaN monolayers on Cu(001) in the rock-salt (RS) and zinc-blende (ZB) structures. Our results indicate that both RS- and ZB-CaN exhibit half-metallic ferromagnetism originated from the incomplete 2p shell of the nitrogen ion. In contrast to the bulk CaN, the CaN monolayers on Cu(001) generally favor ZB structure. We argue that the more stable ZB-CaN thin films on Cu(001) are nonmagnetic, because of strong Cu-N bonding at the interface, while the less stable Ca terminated ZB-CaN thin films exhibit half-metallic ferromagnetism. The transition path between the high energy ferromagnetic and the stable nonmagnetic configurations of the ZB-CaN monolayer on Cu(001) are studied by using the nudged elastic band method. We observe a two stages transition and an activation barrier of about 1.18 eV in the minimum energy path of this transition.

  16. Synthesis, Characterization, Spectral Studies and Antifungal Activity of Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) Complexes with 2-(4- Sulphophenylazo)-1,8-Dihydroxy-3,6-Napthalene Disulphonic Acid Trisodium Salt

    PubMed Central

    Pandey, Gajanan; Narang, K. K.

    2005-01-01

    Complexes of the type Na6[M(HL)2(H2O)2], where M= Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) and Na3H2L= 2-(4-sulphophenylazo)-1,8-dihydroxy 3,6 naphthalene disulphonic acid trisodium salt, have been synthesized and characterized by physico-chemical (elemental analyses, solubility, electrolytic conductance, magnetic susceptibility measurement) and spectral (UV-Visible, IR, ESR, powder x-ray diffraction) techniques for their structure and studied for their antifungal activity against ten fungi. The anionic 1:2 metal:ligand complexes show octahedral geometry around M(II), a significant antifungal activity against Curvularia lunata and Alternaria triticina and a moderate activity against Alternaria brassicicola, Alternaria brassicae, Alternaria solanae, Curvularia species, Helminthosporium oryzae, Collectotrichum capsici, Aspergillus niger, Aspergillus flavus and Fusarium udum. PMID:18365101

  17. The evolution of the polycrystalline copper surface, first to Cu(111) and then to Cu(100), at a fixed CO₂RR potential: a study by operando EC-STM.

    PubMed

    Kim, Youn-Geun; Baricuatro, Jack Hess; Javier, Alnald; Gregoire, John Mathew; Soriaga, Manuel P

    2014-12-23

    A study based on operando electrochemical scanning tunneling microscopy (EC-STM) has shown that a polycrystalline Cu electrode held at a fixed negative potential, -0.9 V (vs SHE), in the vicinity of CO2 reduction reactions (CO2RR) in 0.1 M KOH, undergoes stepwise surface reconstruction, first to Cu(111) within 30 min, and then to Cu(100) after another 30 min; no further surface transformations occurred after establishment of the Cu(100) surface. The results may help explain the Cu(100)-like behavior of Cu(pc) in terms of CO2RR product selectivity. They likewise suggest that products exclusive to Cu(100) single-crystal electrodes may be generated through the use of readily available inexpensive polycrystalline Cu electrodes. The study highlights the dynamic nature of heterogeneous electrocatalyst surfaces and also underscores the importance of operando interrogations when structure-composition-reactivity correlations are intended. PMID:25489793

  18. Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

    SciTech Connect

    Fazleev, N. G.; Weiss, A. H.

    2013-04-19

    In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

  19. XANES and EXAFS study of Au-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1990-01-01

    The near-edge structure (XANES) of the Au L3 and Cu K edges of YBa2Au(0.3)Cu(2.7)O(7-delta) was studied. X ray diffraction suggests that Au goes on the Cu(1) site and XANES shows that this has little effect on the oxidation state of the remaining copper. The gold L3 edge develops a white line feature whose position lies between that of trivalent gold oxide (Au2O3) and monovalent potassium gold cyanide (KAu(CN)2) and whose intensity relative to the edge step is smaller than in the two reference compounds. The L3 EXAFS for Au in the superconductor resembles that of Au2O3. However, differences in the envelope of the Fourier filtered component for the first shell suggest that the local structure of the Au in the superconductor is not equivalent to Au2O3.

  20. Chemisorption of NCO on Cu(1 0 0): A density functional theory study

    NASA Astrophysics Data System (ADS)

    Garda, Graciela R.; Ferullo, Ricardo M.; Castellani, Norberto J.

    2005-12-01

    The isocyanate group adsorption on sites of different coordination of Cu(1 0 0) was theoretically studied considering the cluster approach. The site of four-fold symmetry is the most favored. When NCO adsorbs on Cu, it charges negatively. This electron transfer from the substrate is greater for the site of lowest coordination. The projected DOS curves for the most important valence molecular orbitals of isocyanate group indicate a strong mixing between its 2π orbital and 3d xz and 3d yz AOs of Cu. The predicted asymmetric mode at 2187 cm -1 for NCO adsorbed on the hollow site agrees very well with the experimental observed values of 2162-65 cm -1.

  1. Resonant Inelastic X-ray Scattering Study of the Electronic Structure of Cu2O

    SciTech Connect

    Hill, J.P.; Kim, Y.-J.; Yamaguchi, H.; Gog, T.; Casa, D.

    2010-05-15

    A resonant inelastic x-ray scattering study of the electronic structure of the semiconductor cuprous oxide, Cu{sub 2}O, is reported. When the incident x-ray energy is tuned to the CuK-absorption edge, large enhancements of the spectral features corresponding to the electronic transitions between the valence band and the conduction band are observed. A feature at 6.5 eV can be well described by an interband transition from occupied states of mostly Cu3d character to unoccupied states with mixed 3d, 4s, and O2p character. In addition, an insulating band gap is observed, and the momentum dependence of the lower bound is measured along the {Gamma}-R direction. This is found to be in good agreement with the valence-band dispersion measured with angle-resolved photoemission spectroscopy.

  2. Experimental and Theoretical Studies on Oxidation of Cu-Au Alloy Surfaces: Effect of Bulk Au Concentration

    PubMed Central

    Okada, Michio; Tsuda, Yasutaka; Oka, Kohei; Kojima, Kazuki; Diño, Wilson Agerico; Yoshigoe, Akitaka; Kasai, Hideaki

    2016-01-01

    We report results of our experimental and theoretical studies on the oxidation of Cu-Au alloy surfaces, viz., Cu3Au(111), CuAu(111), and Au3Cu(111), using hyperthermal O2 molecular beam (HOMB). We observed strong Au segregation to the top layer of the corresponding clean (111) surfaces. This forms a protective layer that hinders further oxidation into the bulk. The higher the concentration of Au in the protective layer formed, the higher the protective efficacy. As a result, of the three Cu-Au surfaces studied, Au3Cu(111) is the most stable against dissociative adsorption of O2, even with HOMB. We also found that this protective property breaks down for oxidations occurring at temperatures above 300 K. PMID:27516137

  3. Experimental and Theoretical Studies on Oxidation of Cu-Au Alloy Surfaces: Effect of Bulk Au Concentration.

    PubMed

    Okada, Michio; Tsuda, Yasutaka; Oka, Kohei; Kojima, Kazuki; Diño, Wilson Agerico; Yoshigoe, Akitaka; Kasai, Hideaki

    2016-01-01

    We report results of our experimental and theoretical studies on the oxidation of Cu-Au alloy surfaces, viz., Cu3Au(111), CuAu(111), and Au3Cu(111), using hyperthermal O2 molecular beam (HOMB). We observed strong Au segregation to the top layer of the corresponding clean (111) surfaces. This forms a protective layer that hinders further oxidation into the bulk. The higher the concentration of Au in the protective layer formed, the higher the protective efficacy. As a result, of the three Cu-Au surfaces studied, Au3Cu(111) is the most stable against dissociative adsorption of O2, even with HOMB. We also found that this protective property breaks down for oxidations occurring at temperatures above 300 K. PMID:27516137

  4. TL-OSL study of Li{sub 3}PO{sub 4}: Mg, Cu phosphor

    SciTech Connect

    Rahangdale, S. R. Wankhede, S. P.; Dhabekar, B. S.; Palikundwar, U. A.; Moharil, S. V.

    2015-08-28

    In the present work, we report the thermoluminescence and optically stimulated luminescence properties of Mg and Cu doped Li{sub 3}PO{sub 4} phosphor. The phosphor was synthesized by precipitation method. The thermoluminescence dosimetric peak temperature for the phosphor varies with concentrations of Mg and Cu. Li{sub 3}PO{sub 4} shows good response to 470nm optical stimulation. The OSL sensitivity of the phosphor is approximately 12 times than that of standard Lithium magnesium phosphate. This study may help to develop this material for the application in real time dosimetry using optically stimulated luminescence.

  5. TL-OSL study of Li3PO4: Mg, Cu phosphor

    NASA Astrophysics Data System (ADS)

    Rahangdale, S. R.; Wankhede, S. P.; Dhabekar, B. S.; Palikundwar, U. A.; Moharil, S. V.

    2015-08-01

    In the present work, we report the thermoluminescence and optically stimulated luminescence properties of Mg and Cu doped Li3PO4 phosphor. The phosphor was synthesized by precipitation method. The thermoluminescence dosimetric peak temperature for the phosphor varies with concentrations of Mg and Cu. Li3PO4 shows good response to 470nm optical stimulation. The OSL sensitivity of the phosphor is approximately 12 times than that of standard Lithium magnesium phosphate. This study may help to develop this material for the application in real time dosimetry using optically stimulated luminescence.

  6. XPS and AES Studies of Cu/CdTe(111)-B

    SciTech Connect

    Teeter, G.; Gessert, T. A.; Asher, S. E.

    2005-01-01

    Copper is frequently used as a p-type dopant to improve the performance of back contacts in CdTe thin-film solar cells. In this study, surface-analysis techniques are used to probe fundamental interactions between Cu and the CdTe(111)-B surface. The results presented here were facilitated by the newly constructed surface-analysis cluster tool in the Measurements and Characterization Division at NREL; they reveal a host of fundamental phenomena that occur in the Cu/CdTe system.

  7. ESR dating of barite in sea-floor hydrothermal sulfide deposits at Okinawa Trough

    NASA Astrophysics Data System (ADS)

    Fujiwara, T.; Toyoda, S.; Uchida, A.; Ishibashi, J.; Nakai, S.; Takamasa, A.

    2013-12-01

    The temporal change of submarine hydrothermal activities has been an important issue in the aspect of the evolution of hydrothermal systems which is related with ore formation and biological systems sustained by the chemical species arising from hydrothermal activities (Macdonald et al., 1980). With this aspect, Okumura et al. (2010) made the first practical application of ESR (electron spin resonance) dating technique to a sample of submarine hydrothermal barite to obtain preliminary ages, while Kasuya et al. (1991) first pointed out that barite can be used for ESR dating. ESR is a method to observe radicals having unpaired electrons. As natural radiation creates unpaired electrons in minerals, the age is deduced by dividing the natural radiation dose (obtained from the amount of unpaired electrons) by the dose rate which is estimated by the amount of environmental radioactive elements. The samples were taken by the research cruises, NT12-10 and NT11-20 and NT12-06 operated by JAMSTEC from Hatoma, Yoron, Izena, North Iheya, and Yonaguni IV Knolls of Okinawa Trough. The blocks of sulfide deposits were cut into pieces, and about 2.0g was crushed. The samples were soaked in 12M hydrochloric acid, left for approximately 24 hours. Then, 13M nitric acid was added. Finally, after rinsing in distilled water, the sample was filtered and dried. Impurities were removed by handpicking. A X-ray diffraction study was made to confirm that the grains are pure barite. After γ-ray irradiation at Takasaki Advanced Radiation Research Institute, Japan Atomic Energy Agency, they were measured at room temperature with an ESR spectrometer (JES-PX2300) with a microwave power of 1mW, and the magnetic field modulation amplitude of 0.1mT. The equivalent natural radiation doses were obtained from the increase of ESR signal intensity of SO3- by irradiation. The bulk Ra concentration was measured by the low background pure Ge gamma ray spectrometer. Assuming that Ra is populated only in barite

  8. A DFT study on the Cu (1 1 1) surface for ethyl acetate synthesis from ethanol dehydrogenation

    NASA Astrophysics Data System (ADS)

    Li, Ruzhen; Zhang, Minhua; Yu, Yingzhe

    2012-07-01

    Copper-based catalysts have shown excellent catalytic performances. Despite extensive studies in the field, the microscopic mechanism of ethanol dehydrogenation to ethyl acetate (EA) on Cu-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Cu, density functional theory (DFT) calculations have been performed to study the elementary reactions involved in ethanol dehydrogenation to EA on Cu surfaces. In this work, the adsorption properties of ethanol, ethoxy, acetaldehyde, acetyl and EA on the Cu (1 1 1) catalyst surface were investigated. Based on two pathways, many transition states involved are located. The results show that the route proposed by Colley is more likely to happen.

  9. Microstructural study on Kirkendall void formation in Sn-containing/Cu solder joints during solid-state aging.

    PubMed

    Liu, Zhi-Quan; Shang, Pan-Ju; Tan, Feifei; Li, Douxing

    2013-08-01

    Kirkendall void formation at the solder/metallization interface is an important reliability concern for Cu conductors and under-bump metallization in microelectronic packaging industry, whose mechanism is still hard to be understood for different individual cases. In the present work, two typical solder/Cu-diffusing couples, eutectic SnIn/Cu and SnBi/Cu, were studied by scanning/transmission electron microscopy to investigate the microstructural evolution and voiding process after soldering and then solid-state aging. It was concluded that Kirkendall voids formed between two sublayers within Cu2(In,Sn) phase in eutectic SnIn/Cu solder joint, whereas they appeared at the Cu3Sn/Cu interface or within Cu3Sn for eutectic SnBi/Cu solder joint. Besides the effect of impurity elements, the morphological difference within one intermetallic compound layer could change the diffusing rates of reactive species, hence resulting in void formation in the reaction zone. PMID:23920185

  10. An Endogenous Electron Spin Resonance (ESR) Signal Discriminates Nevi from Melanomas in Human Specimens: A Step Forward in Its Diagnostic Application

    PubMed Central

    Cesareo, Eleonora; Korkina, Liudmila; D’Errico, Gerardino; Vitiello, Giuseppe; Aguzzi, Maria Simona; Passarelli, Francesca; Pedersen, Jens Z.; Facchiano, Antonio

    2012-01-01

    Given the specific melanin-associated paramagnetic features, the Electron Spin Resonance (ESR, called also Electron Paramagnetic Resonance, EPR) analysis has been proposed as a potential tool for non-invasive melanoma diagnosis. However, studies comparing human melanoma tissues to the most appropriate physiological counterpart (nevi) have not been performed, and ESR direct correlation with melanoma clinical features has never been investigated. ESR spectrum was obtained from melanoma and non-melanoma cell-cultures as well as mouse melanoma and non-melanoma tissues and an endogenous ESR signal (g = 2.005) was found in human melanoma cells and in primary melanoma tissues explanted from mice, while it was always absent in non-melanoma samples. These characteristics of the measured ESR signal strongly suggested its connection with melanin. Quantitative analyses were then performed on paraffin-embedded human melanoma and nevus sections, and validated on an independent larger validation set, for a total of 112 sections (52 melanomas, 60 nevi). The ESR signal was significantly higher in melanomas (p = 0.0002) and was significantly different between “Low Breslow’s and “High Breslow’s” depth melanomas (p<0.0001). A direct correlation between ESR signal and Breslow’s depth, expressed in millimetres, was found (R = 0.57; p<0.0001). The eu/pheomelanin ratio was found to be significantly different in melanomas “Low Breslow’s” vs melanomas “High Breslow’s” depth and in nevi vs melanomas “High Breslow’s depth”. Finally, ROC analysis using ESR data discriminated melanomas sections from nevi sections with up to 90% accuracy and p<0.0002. In the present study we report for the first time that ESR signal in human paraffin-embedded nevi is significantly lower than signal in human melanomas suggesting that spectrum variations may be related to qualitative melanin differences specifically occurring in melanoma cells. We therefore conclude that

  11. Edge Stabilized Ribbon (ESR); Stress, Dislocation Density and Electronic Performance

    NASA Technical Reports Server (NTRS)

    Sachs, E. M.

    1984-01-01

    The edge stabilized ribbon (ESR) silicon ribbon was grown in widths of 1, 2.2 and 4.0 inches at speeds ranging from .6 to 7 in/min, which result in ribbon thicknesses of 5 to 400 microns. One of the primary problems remaining in ESR growth is that of thermally induced mechanical stresses. This problem is manifested as ribbon with a high degree of residual stress or as ribbon with buckled ribbon. Thermal stresses result in a high dislocation density in the grown material, resulting in compromised electronic performance. Improvements in ribbon flatness were accomplished by modification of the ribbon cooling profile. Ribbon flatness and other experimental observations of ESR ribbon are discussed. Laser scanner measurements show a good correlation between diffusion length and dislocation density which indicates that the high dislocation densities are the primary cause of the poor current performance of ESR materials. Dislocation densities were reduced and improved electronic performance resulted. Laser scanner data on new and old material are presented.

  12. Kinetic study of CO oxidation over CuO/MO2 (M = Si, Ti and Ce) catalysts

    NASA Astrophysics Data System (ADS)

    Lu, Ji-Qing; Sun, Chong-Xiang; Li, Na; Jia, Ai-Pin; Luo, Meng-Fei

    2013-12-01

    A series of supported CuO/MO2 catalysts (M = Si, Ti and Ce) were prepared using a chemisorption-hydrolysis method and tested for CO oxidation. Kinetic study was carried out to investigate reaction pathways on these catalysts. The power-rate law reaction expressions over CuO/SiO2, CuO/TiO2 and CuO/CeO2 were r = 1.78 × 10-7Pco0.85Po20.22, r = 1.62 × 10-7Pco0.65Po20.19 and r = 1.5 × 10-7Pco0.7Po20, respectively. Activation energies were calculated to be 74.8, 53.4 and 46.3 kJ mol-1 for the CuO/SiO2, CuO/TiO2 and CuO/CeO2 catalysts respectively. Elementary steps of CO oxidation were also proposed. For the CuO/SiO2 catalysts, a Langmuir-Hinshelwood (L-H) model involving chemisorption of CO and O2 on surface Cu atoms was proposed; for the CuO/TiO2 catalysts, a L-H model involving chemisorption of CO on Cu atoms and chemisorption of O2 on TiO2 was proposed, which resulted in a interfacial reaction between the two species. For the CuO/CeO2 catalysts, a Mars van-Krevelen model involving chemisorbed CO on Cu atoms reacting with lattice oxygen in CeO2 was proposed. Effect of CuO particle size was also evaluated. It was found that the active site on the periphery of the CuO-TiO2 and CuO-CeO2 interface was more active on large CuO crystallite than that on small one. The enhanced activity could be interpreted by the higher concentration of chemisorbed CO on the active site on the larger CuO crystallite.

  13. Experimental and theoretical studies of highly emissive dinuclear Cu(I) halide complexes with delayed fluorescence.

    PubMed

    Kang, Liju; Chen, Jin; Teng, Teng; Chen, Xu-Lin; Yu, Rongmin; Lu, Can-Zhong

    2015-07-01

    A series of luminescent homo-dinuclear Cu(I) halide complexes, [PPh2PAr2Cu(μ-X)2CuPPh2PAr2] (X = I (1), Br (2), Cl (3)) (PPh2PAr2 = (1-bis(2-methylphenyl)phosphino-2-diphenylphosphino)benzene) were synthesized from the reaction of the corresponding cuprous halide and the chelating bisphosphine ligand PPh2PAr2 in CH3CN. The complexes were structurally characterized by X-ray single crystal analysis. Their photophysical properties were studied in detail. The Cu(I) atoms in these complexes are four-coordinated and adopt a tetrahedral coordination geometry. In each complex, the copper centers are bridged by two halide anions and each Cu(I) is chelated further terminally by a PPh2PAr2 ligand. The[Cu(μ-X)2Cu] cores have similar butterfly-type configurations. The distances between the Cu(I) atoms in each complex are over 2.94 Å. In the solid state, these complexes are highly emissive and exhibit bluish-green photoluminescence (emission peaks, λmax = 488 nm (1), 482 nm (2), 490 nm (3)) with short lifetimes (4.9-5.9 μs) and high quantum yields (ϕ = 0.42-0.95) at room temperature. In this series of complexes, the ligand-field strengths of the ions (I(-) < Br(-) < Cl(-)) do not have obvious effect on the emission maxima. The studies on varied temperature emission spectra and decay behaviours of these complexes indicate that the mechanism of their emissions involves two thermal-equilibrium excited states. At room temperature, the complexes display thermally activated delayed fluorescences with short decay lifetimes. With a decrease of the temperature, a significant increase of emission decay times by almost 2 orders of magnitude is observed. At temperatures below T ≈ 100 K, the decay times of the studied complexes are over one hundred microseconds long, which indicates that the emission originates mainly from the triplet state (T1 state). To interpret the varied temperature photophysics of these complexes, an equilibrated 2 excited states model S0 ← T1 ↔ S1 → S0

  14. Study of tribological behavior of Cu-MoS2 and Ag-MoS2 nanocomposite lubricants.

    PubMed

    An, V; Anisimov, E; Druzyanova, V; Burtsev, N; Shulepov, I; Khaskelberg, M

    2016-01-01

    Tribological behavior of Cu-MoS2 and Ag-MoS2 nanocomposite lubricant was studied. Cu nanoparticles produced by electrical explosion of copper wires and Ag nanoparticles prepared by electrospark erosion were employed as metal cladding modifiers of MoS2 nanolamellar particles. The tribological tests showed Cu-MoS2 and Ag-MoS2 nanocomposite lubricants changed the friction coefficient of the initial grease and essentially improved its wear resistance. PMID:26837277

  15. Antiferromagnetism in Co-57-doped La2CuO(4-y) studied by Moessbauer spectroscopy

    NASA Technical Reports Server (NTRS)

    Jha, S.; Mitros, C.; Lahamer, Amer; Yehia, Sherif; Julian, Glenn M.

    1989-01-01

    Moessbauer effect studies of Co-57-doped La2CuO(4-y) were performed at temperatures between 4.2 K and room temperature. These confirm the antiferromagnetic ordering of these compounds below room temperature. Temperature dependence of the quadrupole splitting shows that the hyperfine field is at an angle with the c-axis.

  16. Cross-sectional TEM studies of DIGM in irradiated Au-Cu bilayers

    SciTech Connect

    Gao, Y.; Alexander, D.E.; Rehn, L.E.

    1992-11-01

    Cross-sectional transmission electron microscopy was used to study diffusion-induced gain boundary migration (DIGM) in irradiated and annealed Au/Cu bilayers. Using this technique, in combination with small probe x-ray energy dispersive spectroscopy, DIGM alloyed zones in Au were identified in an irradiated sample.

  17. Growth of Co films on Cu(111) studied in real space

    NASA Astrophysics Data System (ADS)

    Hochstrasser, M.; Zurkirch, M.; Wetli, E.; Pescia, D.; Erbudak, M.

    1994-12-01

    The atomic structure of Co films deposited on Cu(111) at room temperature is studied by imaging backscattered secondary electrons. The patterns show in-registry growth for the first two atomic layers. The next two monolayers show features of the fcc as well as the hcp structure. The hexagonal structure characteristic for bulk Co is found for subsequent layers.

  18. Germline ESR2 mutation predisposes to medullary thyroid carcinoma and causes up-regulation of RET expression.

    PubMed

    Smith, Joel; Read, Martin L; Hoffman, Jon; Brown, Rachel; Bradshaw, Beth; Campbell, Christopher; Cole, Trevor; Navas, Johanna Dieguez; Eatock, Fiona; Gundara, Justin S; Lian, Eric; Mcmullan, Dom; Morgan, Neil V; Mulligan, Lois; Morrison, Patrick J; Robledo, Mercedes; Simpson, Michael A; Smith, Vicki E; Stewart, Sue; Trembath, Richard C; Sidhu, Stan; Togneri, Fiona S; Wake, Naomi C; Wallis, Yvonne; Watkinson, John C; Maher, Eamonn R; McCabe, Christopher J; Woodward, Emma R

    2016-05-01

    Familial medullary thyroid cancer (MTC) and its precursor, C cell hyperplasia (CCH), is associated with germline RET mutations causing multiple endocrine neoplasia type 2. However, some rare families with apparent MTC/CCH predisposition do not have a detectable RET mutation. To identify novel MTC/CCH predisposition genes we undertook exome resequencing studies in a family with apparent predisposition to MTC/CCH and no identifiable RET mutation. We identified a novel ESR2 frameshift mutation, c.948delT, which segregated with histological diagnosis following thyroid surgery in family members and demonstrated loss of ESR2-encoded ERβ expression in the MTC tumour. ERα and ERβ form heterodimers binding DNA at specific oestrogen-responsive elements (EREs) to regulate gene transcription. ERβ represses ERα-mediated activation of the ERE and the RET promoter contains three EREs. In vitro, we showed that ESR2 c.948delT results in unopposed ERα mediated increased cellular proliferation, activation of the ERE and increased RET expression. In vivo, immunostaining of CCH and MTC using an anti-RET antibody demonstrated increased RET expression. Together these findings identify germline ESR2 mutation as a novel cause of familial MTC/CCH and provide important insights into a novel mechanism causing increased RET expression in tumourigenesis. PMID:26945007

  19. Structural, EPR, optical and Raman studies of Nd2O3:Cu2+ nanophosphors.

    PubMed

    Umesh, B; Eraiah, B; Nagabhushana, H; Sharma, S C; Nagabhushana, B M; Shivakumara, C; Rao, J L; Chakradhar, R P S

    2012-08-01

    Nanocrystalline Nd(2)O(3):Cu(2+) (2mol %) phosphors have been prepared by a low temperature solution combustion technique. Powder X-ray diffraction (PXRD) results confirm that hexagonal A-type Nd(2)O(3) (900°C, 3h) and the lattice parameters have been evaluated by Rietveld refinement. Surface morphology of as-formed and Cu(2+) doped Nd(2)O(3) phosphors show that the particles are irregular in shape and porous in nature. TEM results also confirm the nature and size of the particles. The EPR spectrum exhibits two resonance signals with effective g values at g(ǀǀ)≈2.12 and g(⊥)≈2.04. The g values indicate that the site symmetry of Cu(2+) ions is octahedral symmetry with elongated tetragonal distortion. Raman studies show major peaks, which are assigned, to F(g) and combination of A(g)+E(g) modes. It is observed that the Raman peaks and intensity have been reduced in Cu(2+) doped samples. UV-Visible absorption spectra exhibit a strong and broad absorption band at ∼240nm. Further, the absorption peak shifts to ∼14nm in Cu(2+) doped samples. The optical band gap is estimated to be 5.28eV for Cu doped Nd(2)O(3) nanoparticles which are higher than the bulk Nd(2)O(3) (4.7eV). This can be attributed to the quantum confinement effect of the nanoparticles. PMID:22579331

  20. ESR dating of Neogene marine sands from the southern North Sea basin, NE Belgium: first results

    NASA Astrophysics Data System (ADS)

    Iacovo, Serena; Jivanescu, Mihaela; Beerten, Koen; Stesmans, Andre; Vandenberghe, Noël

    2013-04-01

    Quantifying Neogene and Quaternary geodynamic processes requires reliable age control on the geological record from which the rate and intensity of these processes are usually derived. The nature and geometry of marine sediments preserved in the southern North Sea basin, NE Belgium, are influenced by geodynamic processes such as tectonic movements and eustatic sea level changes. Yet, the geochronology of these sediments is almost entirely based on micropalaeontological analyses and subsequent correlations with widely accepted geological boundaries. In recent years, the electron spin resonance (ESR) dating method has been applied to buried sediments that range in age between ~ 100 ka and several Ma. The method is based on the measurement of accumulated radiation damage in quartz crystals during burial, and can thus in theory be applied to obtain absolute numerical age control on any quartz-rich sediment given several conditions are met. The most important of these is sunlight bleaching of pre-existing radiation damage prior to burial. In this case study, we present preliminary ESR dating results of three samples from a cored borehole in Miocene glauconite-rich sands, which are biostratigraphically estimated as between 7 Ma and 11 Ma (Tortonian). Following chemical and physical purification of the samples (taken at 107 m, 135 m and 147 m depth), quartz grains (100-200 µm) were irradiated by Co-60 gamma rays to doses between 1-150 kGy. Individual aliquots (each weighting several 100 mg) were measured at cryogenic temperatures in a JEOL X-band ESR spectrometer operating at a microwave frequency of ~ 9.2 GHz. Defect densities were derived by integration of relevant ESR spectra, and making use of a comounted defect density calibrated marker sample. Subsequently, the equivalent dose was calculated using the thus constructed dose curves (including the natural, unirradiated, aliquot). Finally, dose rates were determined using high resolution gamma ray spectrometry in the

  1. In Situ XANES Study of CuO/TiO2 Thin Films During Photodegradation of Methylene Blue

    SciTech Connect

    Hsiung Tungli; Wang, H. Paul; Wei Yuling

    2007-02-02

    Speciation of copper in the CuO/TiO2 thin film (synthesized by the doctor-blade deposition method) during photocatalytic decomposition of methylene blue has been studied by in situ X-ray absorption near-edge structural (XANES) spectroscopy. During the UV/VIS radiation (90 min), in the presence of methylene blue, a decrease of Cu(II) and an increases of Cu(0) and Cu(I) fractions in the CuO/TiO2 thin film are observed by in situ XANES. The r-space Fourier transformation EXAFS (extend X-ray absorption fine structural) spectra also show that the bond distance of Cu-O in the thin film is decreased by 0.03 A during photocatalytic degradation of methylene blue.

  2. Crystal and Electronic Study of Neodymium-Substituted CuFeO2 Oxide

    NASA Astrophysics Data System (ADS)

    Ozkendir, Osman Murat

    2016-06-01

    Neodymium-substituted CuFeO2 samples were investigated according to their crystal and electronic properties via the general formula Nd x Cu1- x FeO2. The crystal structure analysis results revealed polycrystalline formations in the sample and a change in crystalline sizes with the substituted heavy fermion "Nd." Increasing the Nd amount in the sample was determined to cause a disturbance on the Cu-Fe planes that supports the formation of crystal structures with low crystal symmetries such as monoclinic or triclinic geometries. To obtain the background mechanisms of the crystal properties, the X-ray absorption fine structure spectroscopy technique was used to study the electronic properties of the samples. Prominent changes in the crystal structures due to 4 f electrons' contributions from the substituted Nd atoms as the main "role player" in the phase transitions were determined. The Nd atoms were observed as the key element guiding the entire phenomenon as a result of their large size and narrow 4 f levels. Also, magnetic properties of the samples were tested at room temperature and without an applied magnetic field by X-ray magnetic circular dichroism study due to previous studies that reported the parent oxide CuFeO2 to have magnetic ordering at T N = 11 K (-262 °C). Except the sample for x = 1.0 (NdFeO3), no magnetic ordering was observed at room temperature; i.e., all of the samples showed paramagnetic behaviors.

  3. Cu(2+) and Fe(2+) mediated photodegradation studies of soil-incorporated chlorpyrifos.

    PubMed

    Rafique, Nazia; Tariq, Saadia R; Ahad, Karam; Taj, Touqeer

    2016-03-01

    The influences of Cu(2+) and Fe(2+) on the photodegradation of soil-incorporated chlorpyrifos were investigated in the present study. The soil samples spiked with chlorpyrifos and selected metal ions were irradiated with UV light for different intervals of time and analyzed by HPLC. The unsterile and sterile control soil samples amended with pesticides and selected metals were incubated in the dark at 25 °C for the same time intervals. The results of the study evidenced that photodegradation of chlorpyrifos followed the first-order kinetics. The dissipation t0.5 of chlorpyrifos was found to decrease from 41 to 20 days under UV irradiation. The rate of chlorpyrifos photodegradation was increased in the presence of both metals, i.e., Cu(2+) and Fe(2+). Thus, initially observed t0.5 of 19.8 days was decreased to 4.39 days in the case of Cu(+2) and 19.25 days for Fe(+2). Copper was found to increase the rate of photodegradation by 4.5 orders of magnitude while the microbial degradation of chlorpyrifos was increased only twofold. The microbial degradation of chlorpyrifos was only negligibly affected by Fe(2+) amendment. The studied trace metals also affected the abiotic degradation of the pesticide in the order Cu(2+) > Fe(2+). PMID:26507736

  4. A DFT study on CO oxidation catalyzed by subnanometer AlCu n ( n = 1-3) clusters

    NASA Astrophysics Data System (ADS)

    Dong, Xiaona; Guo, Ling; Wen, Caixia; Ren, Ningning; Niu, Shuangshu

    2014-07-01

    Through the first-principle density-functional theory (DFT) calculations, we have made an exhaustive study of the mechanism of CO oxidation catalyzed by AlCu n ( n = 1-3) clusters on gas phase. It is shown that mixing two different metals (Al and Cu) can have beneficial effects on the catalytic activity than monometallic Cu n + 1 ( n = 1-3) cluster toward the reaction of CO oxidation and the alloyed AlCu3 cluster is proposed as the best effective nanocatalysts.

  5. Synthesis and spectral feature of benzophenone-substituted thiosemicarbazones and their Ni(II) and Cu(II) complexes

    NASA Astrophysics Data System (ADS)

    El-Asmy, A. A.; Al-Hazmi, G. A. A.

    2009-01-01

    The ligational behavior of 2-hydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone N-substituted thiosemicarbazones towards Ni(II) and Cu(II) ions has been investigated. The isolated complexes were identified by elemental analyses, molar conductance, magnetic moment, IR, UV-vis and ESR spectral studies. The IR spectra indicated that the investigated thiosemicarbazones lost the N 2 proton or the N 2 and OH protons and act as mononegative or binegative tridentate ligands. The ligands containing methoxy group facilitate the deprotonation of OH by resonance more than the SH. Most of the Ni(II) complexes measured subnormal magnetic moments due to square-planar + tetrahedral configuration and supported by the electronic spectra. The percentage of square-planar to tetrahedral was calculated and found in agreement with the ligand splitting energy (10Dq). Also, Cu(II) complexes measured subnormal values due to the interaction between copper centers; the lower the value the higher the interaction. It was found that the substitutent has a noticeable effect on the distortion of the complex. The ESR spectra of some solid Cu(II) complexes at room temperature exhibit g|| > g⊥ > 2.0023 confirming a square-planar structure.

  6. Magnetic excitations in the spin-1/2 triangular-lattice antiferromagnet Cs2CuBr4

    DOE PAGESBeta

    Zvyagin, S. A.; Ozerov, M.; Kamenskyi, D.; Wosnitza, J.; Krzystek, J.; Yoshizawa, D.; Hagiwara, M.; Hu, Rongwei; Ryu, Hyejin; Petrovic, C.; et al

    2015-11-27

    We present on high- field electron spin resonance (ESR) studies of magnetic excitations in the spin- 1/2 triangular-lattice antiferromagnet Cs2CuBr4. Frequency- field diagrams of ESR excitations are measured for different orientations of magnetic fields up to 25 T. We show that the substantial zero- field energy gap, Δ ≈ 9.5 K, observed in the low-temperature excitation spectrum of Cs2CuBr4 [Zvyagin et al:, Phys. Rev. Lett. 112, 077206 (2014)], is present well above TN. Noticeably, the transition into the long-range magnetically ordered phase does not significantly affect the size of the gap, suggesting that even below TN the high-energy spin dynamicsmore » in Cs2CuBr4 is determined by short-range-order spin correlations. The experimental data are compared with results of model spin-wave-theory calculations for spin-1/2 triangle-lattice antiferromagnet.« less

  7. 63Cu-NMR study of oxygen disorder in ortho-II YBa2Cu3Oy

    NASA Astrophysics Data System (ADS)

    Wu, T.; Zhou, R.; Hirata, M.; Vinograd, I.; Mayaffre, H.; Liang, R.; Hardy, W. N.; Bonn, D. A.; Loew, T.; Porras, J.; Haug, D.; Lin, C. T.; Hinkov, V.; Keimer, B.; Julien, M.-H.

    2016-04-01

    We show that 63Cu-NMR spectra place strong constraints on both the nature and the concentration of oxygen defects in ortho-II YBa2Cu3Oy . Systematic deviation from ideal ortho-II order is revealed by the presence of inequivalent Cu sites in either full or empty chains. The results can be explained by two kinds of defects: oxygen clustering into additional chains, or fragments thereof, most likely present at all concentrations (6.4

  8. Adsorption studies of Cu(II) onto biopolymer chitosan and its nanocomposite 5%bentonite/chitosan.

    PubMed

    Moussout, Hamou; Ahlafi, Hammou; Aazza, Mustapha; Zegaoui, Omar; El Akili, Charaf

    2016-01-01

    Chitosan (CS) and nanocomposite 5%bentonite/chitosan (5%Bt/CS) prepared from the natural biopolymer CS were tested to remove Cu(II) ions using a batch adsorption experiment at various temperatures (25, 35 and 45°C). X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis/differential thermal analysis (TGA/DTA) were used in CS and the nanocomposite characterisation. This confirmed the exfoliation of bentonite (Bt) to form the nanocomposite. The adsorption kinetics of copper on both solids was found to follow a pseudo-second-order law at each studied temperature. The Cu(II) adsorption capacity increased as the temperature increased from 25 to 45°C for nanocomposite adsorbent but slightly increased for CS. The data were confronted to the nonlinear Langmuir, Freundlich and Redlich-Peterson models. It was found that the experimental data fitted very well the Langmuir isotherm over the whole temperature and concentration ranges. The maximum monolayer adsorption capacity for the Cu(II) was 404-422 mg/g for CS and 282-337 mg/g for 5%Bt/CS at 25-45°C. The thermodynamic study showed that the adsorption process was spontaneous and endothermic. The complexation of Cu(II) with NH(2) and C = O groups as active sites was found to be the main mechanism in the adsorption processes. PMID:27148722

  9. Synthesis, characterization, thermal study and biological evaluation of Cu(II), Co(II), Ni(II) and Zn(II) complexes of Schiff base ligand containing thiazole moiety

    NASA Astrophysics Data System (ADS)

    Nagesh, G. Y.; Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2015-01-01

    The novel Schiff base ligand 2-(4-(dimethylamino)benzylidene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 4-dimethylaminobenzaldehyde and its newly synthesized Cu(II), Co(II), Ni(II) and Zn(II) complexes have been characterized by microanalysis, magnetic susceptibility, molar conductance, thermal analysis, FT-IR, 1H NMR, ESI mass, UV-Visible, ESR spectroscopy and powder X-ray diffraction data. The newly synthesized ligand behaves as a bidentate ON donor. The IR results confirmed the bidentate binding of the ligand involving oxygen atom of amide carbonyl and azomethine nitrogen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties of all the compounds against Artemia salina. Furthermore, the antioxidant activity of the ligand (L) and its metal complexes were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH), the ligand exhibited potent in vitro - antioxidant activity than its metal complexes.

  10. Study of Height Reduction of Sn99Cu1/Cu Solder Joints as a Result of Isothermal Aging

    NASA Astrophysics Data System (ADS)

    Chen, Zhiwen; Liu, Changqing; Wu, Yiping; An, Bing; Zhou, Longzao

    2015-11-01

    Sn99Cu1/Cu solder joints were investigated after isothermal aging at 175°C for different lengths of time under vacuum conditions. The results revealed height reduction of the solder of approximately 1.2 μm after aging for 1132.5 h. This was primarily attributed to growth of a layer of interfacial intermetallic compounds. The reduction was measured by use of a copper block containing a recess filled with solder, which was reflowed then polished flat. Height reduction of the solder joint during aging was found to obey the parabolic law Δ h = -0.031√ t, and was in excellent agreement with theoretical calculation.

  11. Structural Study of Cu-Deficient Cu2(1-x)ZnSnSe4 Solar Cell Materials by X-ray Diffraction and X-ray Absorption Fine Structure

    NASA Astrophysics Data System (ADS)

    Gao, Feng; Yamazoe, Seiji; Maeda, Tsuyoshi; Wada, Takahiro

    2012-10-01

    Cu-poor Cu2(1-x)ZnSnSe4 powders were prepared from elemental powders. The crystal structure of Cu-poor Cu2(1-x)ZnSnSe4 was examined by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. Kesterite-type Cu2(1-x)ZnSnSe4 could be prepared in the range of 0≤x ≤0.0750. The lattice parameters were refined by the Rietveld analysis of X-ray diffraction data. The lattice constants a and c decreased with a decrease in the Cu/(Zn+Sn) ratio. However, there was little change in c/a value. On the other hand, the position of the Se atom (u parameters) changed considerably. The XAFS study showed that the local structure of Sn in Cu2ZnSnSe4 (CZTSe) changed with a decrease in Cu/(Zn+Sn) ratio and the local structural changes in Cu, Zn, or Se could not be clearly observed. These local structural changes around Sn are due to the disordering of Cu, Zn, and Sn atoms. The diffuse reflectance spectra showed that the band gap of Cu2ZnSnSe4 is 0.98 eV and that the band gaps do not depend on Cu/(Zn+Sn) ratio in the range of 0≤x ≤0.0750.

  12. Polymorphisms in CYP17, COMT, and ESR1 genes in women after menopause and association with bone mineral density.

    PubMed

    Gonçalves, C G; Almeida, B C; Camargo-Kosugi, C M; Costa, A M M; Silva, I D C G; Haidar, M A

    2015-01-01

    In this study, we evaluated genetic factors related to the mineral density during post-menopause. We evaluated 110 women in the first 5 years post-menopause, without previous hormone replacement therapy. Cytochrome P450 17 (CYP17) (rs743572), catechol-O-methyl transferase (COMT) (rs4680), and estrogen receptor 1 (ESR1) (rs9322331) were examined for the presence of polymorphisms. Clinical data were collected by anamnesis; all patients had the osseous densitometry examined using a lunar instrument to determine mineral osseous densitometry in the lumbar column (L2-L4). CYP17, COMT, and ESR1 genotyping was carried out by polymerase chain reaction with DNA collected from buccal swabs. The average age was 51.96 years. The average weights of the patients in control and osteopenia groups were 70.25 ± 12.00 and 62.45 ± 11.64, respectively (P = 0.001) and body mass index (P = 0.006; control: 29.43 ± 5.25; osteopenia: 26.72 ± 4.57). Related to CYP17 polymorphisms, 28.18% of women were TT (wild-type homozygous), 60% were TC (heterozygous), and 11.82% were CC (mutated homozygous). Related to COMT polymorphisms, 53.64% of women were GG (wild-type homozygous), 37.27% were GA (heterozygous), and 9.09% were AA (mutated homozygous). Related to ESR1, 53.64% of women were CC (wild-type homozygous), 40.91% were CT (heterozygous), and 5.45% were TT (mutated homozygous). The ESR1 variant allele was significantly higher in the osteopenia group when compared with women in the normal group (P = 0.02). ESR1 may be associated with low mineral osseous densitometry, while CYP17 and COMT gene polymorphisms were not associated with mineral osseous densitometry. PMID:26634548

  13. Density functional theory study of O-H and C-H bond scission of methanol catalyzed by a chemisorbed oxygen layer on Cu(111)

    NASA Astrophysics Data System (ADS)

    Li, Jonathan; Zhou, Guangwen

    2016-04-01

    Using the density-functional theory within the generalized gradient approximation, we have studied the partial oxidation of methanol on a Cu(111) surface covered with a chemisorbed oxygen layer that resembles a Cu2O layer. Adsorption energies and geometries were computed for methanol, methoxy, hydroxymethyl and formaldehyde on both clean Cu(111) and Cu2O/Cu(111) and electronic structures were computed for the reaction intermediates on Cu2O/Cu(111). We also calculated the energy barrier for partial oxidation of methanol to formaldehyde on Cu2O/Cu(111). These results show that the Cu2O monolayer slightly lowers the stability of each of the surface adsorbates and the oxygen strongly promotes hydrogen dissociation by lowering the energy barrier of methanol decomposition and causing the spontaneous dissociation of methanol into methoxy.

  14. Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

    NASA Astrophysics Data System (ADS)

    Moon, Ellen M.; Peacock, Caroline L.

    2011-11-01

    Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

  15. The Cubesat mission to study Solar Particles (CuSP), an interplanetary cubesat

    NASA Astrophysics Data System (ADS)

    Christian, E. R.; Desai, M. I.; Allegrini, F.; Jahn, J. M.; Kanekal, S.; Livi, S. A.; Murphy, N.; Ogasawara, K.; Paschalidis, N.

    2015-12-01

    The Cubesat mission to study Solar Particles (CuSP) is a funded 6U interplanetary cubesat scheduled to fly on the EM-1 SLS launch in 2018. CuSP has three small but capable instruments from the Southwest Research Institute (SwRI), NASA Goddard Space Flight Center (GSFC), and the NASA Jet Propulsion Laboratory (JPL). Its primary scientific goal is high-cadence precise measurements of the suprathermal (ST) tail in the solar wind. The suprathermal tail is the critical bridge between the thermal solar wind plasma and the dangerous high-energy solar energetic particles. CuSP also measures the energy spectra and composition of the ~1-50 MeV/nucleon H-Fe ions that evolve from the STs and the interplanetary magnetic field that is closely coupled to the particle distributions. CuSP is a stepping-stone to future interplanetary cubesats, smallsats, and constellations for both scientific and space weather applications. The challenges for this mission and future missions will also be discussed.

  16. Biosorption of Cu(II) by immobilized microalgae using silica: kinetic, equilibrium, and thermodynamic study.

    PubMed

    Lee, Hongkyun; Shim, Eunjung; Yun, Hyun-Shik; Park, Young-Tae; Kim, Dohyeong; Ji, Min-Kyu; Kim, Chi-Kyung; Shin, Won-Sik; Choi, Jaeyoung

    2016-01-01

    Immobilized microalgae using silica (IMS) from Micractinium reisseri KGE33 was synthesized through a sol-gel reaction. Green algal waste biomass, the residue of M. reisseri KGE33 after oil extraction, was used as the biomaterial. The adsorption of Cu(II) on IMS was tested in batch experiments with varying algal doses, pH, contact times, initial Cu(II) concentrations, and temperatures. Three types of IMSs (IMS 14, 70, and 100) were synthesized according to different algal doses. The removal efficiency of Cu(II) in the aqueous phase was in the following order: IMS 14 (77.0%) < IMS 70 (83.3%) < IMS 100 (87.1%) at pH 5. The point of zero charge (PZC) value of IMS100 was 4.5, and the optimum pH for Cu(II) adsorption was 5. Equilibrium data were described using a Langmuir isotherm model. The Langmuir model maximum Cu(II) adsorption capacity (q m) increased with the algal dose in the following order: IMS 100 (1.710 mg g(-1)) > IMS 70 (1.548 mg g(-1)) > IMS 14 (1.282 mg g(-1)). The pseudo-second-order equation fitted the kinetics data well, and the value of the second-order rate constant increased with increasing algal dose. Gibbs free energies (ΔG°) were negative within the temperature range studied, which indicates that the adsorption process was spontaneous. The negative value of enthalpy (ΔH°) again indicates the exothermic nature of the adsorption process. In addition, SEM-energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS) analyses of the IMS surface reveal that the algal biomass on IMS is the main site for Cu(II) binding. This study shows that immobilized microalgae using silica, a synthesized biosorbent, can be used as a cost-effective sorbent for Cu(II) removal from the aqueous phase. PMID:25953610

  17. Optical and other spectroscopic studies of lead, zinc bismuth borate glasses doped with CuO

    NASA Astrophysics Data System (ADS)

    Rajyasree, Ch.; Vinaya Teja, P. Michael; Murthy, K. V. R.; Krishna Rao, D.

    2011-12-01

    10MO·20Bi2O3·(70-x)B2O3·xCuO [M=Pb, Zn] with x=0, 0.4 and 0.8 (wt%) glasses were synthesized by the melt-quenching technique and were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. Physical parameters, like density, and spectroscopic studies (optical absorption, EPR, FTIR and photoluminescence) were used to understand the role of modifier oxide and CuO in the glass matrix. A red shift of the absorption band corresponds to 2B1g→2B2g transition of Cu2+ ions from P2 to Z4 samples and the increase of hyperfine splitting factor (A‖) from P2 to Z2 shows that with the integration of PbO by ZnO the electron density around copper ion is increased. It is also supported by the gradual increase in theoretical optical basicity values of ZnO mixed glasses, as compared to that of PbO mixed glass matrix. Reduced bismuth radicals are found in undoped and 0.4% CuO doped glasses of both the series. Analysis of the absorption and emission studies indicates that the concentration of luminescence centers of bismuth ions (Bi3+ ions in UV region) is decreased by the integration of ZnO as well as by increasing the dopant concentration. In lead series PbO4 and BiO3 units are increased from P2 to P4 and in zinc series BiO3 units are decreased from Z0 to Z4. The conductivity of the glass matrices is increased in both the series with the dopant of CuO.

  18. ELECTRON SPIN RESONANCE STUDIES ON MELANIN.

    PubMed

    BLOIS, M S; ZAHLAN, A B; MALING, J E

    1964-11-01

    Electron spin resonance (e.s.r.) observations of squid melanin have been conducted over the temperature range 500 degrees K to 4.2 degrees K, and the effect of various chemical treatments of the melanin upon the e.s.r. spectrum has been studied. The findings have shown that the paramagnetism of this melanin follows the Curie Law from 500 degrees K to 4.2 degrees K, that the spin signal can be eliminated by the addition of Cu(++) to the melanin, and that the optical and e.s.r. absorptions of melanin are independent since either can be reduced or eliminated without affecting the other. Similar studies on synthetic melanins produced by autoxidation or by enzymatic oxidation of a number of biphenols were carried out. It was found that the e.s.r. signals of these synthetic melanins were strikingly similar (with respect to line width, line shape, and g-value) with those of squid melanin. It is concluded that the unpaired electrons observed are associated with trapped free radicals in the melanin polymer, that the biosynthesis of melanin may involve a free radical mechanism, and that these physical data are in accord with the concept of Nicolaus that melanin is a highly irregular, three-dimensional, polymer. PMID:14232133

  19. Scanning Tunneling Microscopy Studies of Surface Structures of Icosahedral Al-Cu-Fe Quasicrystals

    SciTech Connect

    Tanhong Cai

    2002-12-31

    Three papers are included in this dissertation. The first paper: ''Structural aspects of the fivefold quasicrystalline Al-Cu-Fe surface from STM and dynamical LEED studies'', is in press with ''Surface Science''. The second paper: ''An STM study of the atomic structure of the icosahedral Al-Cu-Fe fivefold surface'' is submitted to ''Physical Review B, Rapid Communication''. The third paper: ''Pseudomorphic starfish: arrangement of extrinsic metal atoms on a quasicrystalline substrate'' is submitted to ''Nature''. Following the third paper are general conclusions and appendices that document the published paper ''Structural aspects of the three-fold surface of icosahedral Al-Pd-Mn'' (appearing in volume 461, issue 1-3 of ''Surface Science'' on page L521-L527, 2000), the design as well as the specifications of the aluminum evaporator used in the aluminum deposition study in this dissertation, an extended discussion of the aluminum deposition on the quasicrystalline surface, and the STM database.

  20. Diffusion within α-CuI studied using ab initio molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mohn, Chris E.; Stølen, Svein; Hull, Stephen

    2009-08-01

    The structure and dynamics of superionic α-CuI are studied in detail by means of ab initio Born-Oppenheimer molecular dynamics simulations. The extreme cation disorder and a soft immobile face centred cubic sublattice are evident from the highly diffuse atomic density profiles. The Cu-Cu pair distribution function and distribution of Cu-I-Cu bond angles possess distinct peaks at 2.6 Å and 60° respectively, which are markedly lower than the values expected from the average cationic density, pointing to the presence of pronounced short-range copper-copper correlations. Comparison with lattice static calculations shows that these correlations and the marked shift in the cationic density profile in the lang111rang directions are associated with a locally distorted cation sublattice, and that the movements within the tetrahedral cavities involve rapid jumps into and out of shallow basins on the system potential energy surface. On average, the iodines are surrounded by three coppers within their first coordination shell, with the fourth copper being located in a transition zone between two neighbouring iodine cavities. However, time-resolved analysis reveals that the local structure actually involves a mixture of threefold-, fourfold- and fivefold-coordinated iodines. Examination of the ionic trajectories shows that the copper ions jump rapidly to nearest neighbouring tetrahedral cavities (aligned in the lang100rang directions) following a markedly curved trajectory and often involving short-lived (~1 ps) interstitial positions. The nature of the correlated diffusion underlying the unusually high fraction of coppers with short residence time can be attributed to the presence of a large number of 'unsuccessful' jumps and the likelihood of cooperative motion of pairs of coppers. The calculated diffusion coefficient at 750 K, DCu = 2.8 × 10-5 cm2 s-1, is in excellent agreement with that found experimentally.

  1. Two novel Cu(II) diphosphonates: Structural, spectral and magnetic studies

    NASA Astrophysics Data System (ADS)

    Ma, Kui-Rong; Zhang, Yu; Kan, Yu-He; Hu, Hua-You; Cong, Ming-Hui; Zhang, Yong-Jun

    2013-11-01

    By introducing the second organic N-heterocyclic ligands 2,2‧-bipyridine (2,2‧-bipy)/1,10-phenanthroline (phen), two mono-/bi-nuclear examples of Cu(II)-diphosphonate coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H5L = CH3C(OH)(PO3H2)2), [Cu(H4L)2(2,2‧-bipy)]·H2O 1 and [Cu(H3L)(phen)]2·(HOCH2CH2OH)0.52, have been solvothermally obtained and characterized by powder X-ray diffraction, elemental analysis, IR, TG-DSC. The single-crystal X-ray diffractions show that both the two compounds possess zero-dimensional structures, built from mononuclear unit [CuO4N2]n for 1 and binuclear unit [-Cu-O-P-O-]2n with a double O-P-O bridge for 2 in syn-anti fashion. Then H-bond or/and π-π interactions further expand the two zero-dimensional structures into the three-dimensional supramolecular frameworks. Fluorescent measurements reveal that the maximum emission peaks of 1-2 centered at 433.5 nm for 1 and 434.5 nm for 2, respectively, are mainly caused by intraligand π*-π emission state of N-heterocyclic ligands (λex = 235 nm). The further magnetic study shows the two coordination polymers exhibit antiferromagnetic behavior for 1 between the mononuclear units, while ferromagnetic behavior for 2 derived from double O-P-O bridges in syn-anti mode between the metal centers.

  2. First-principles study on the electronic, magnetic and spin transport properties of CU(6bpyNO)Cl2

    NASA Astrophysics Data System (ADS)

    Sun, Guoliang; Ding, J. F.

    2015-11-01

    The electronic structure and magnetic properties of organic Cu(6bpyNO)Cl2 have been studied by using the first-principles calculations based on density-functional theory. It is shown that the total spin magnetic moment per molecule is about 2.00 μB, which mainly comes from the Cu2+. Cu(6bpyNO)Cl2 has a semiconductor characteristic. We also calculate the spin transport properties of Cu(6bpyNO)Cl2 connected with gold electrodes by using the density-functional theory combined with the nonequilibrium Green's function, and find it exhibits nearly 100% spin polarization and obvious negative differential resistance effect, which are explained by the calculated spin-polarized transmission spectra. These studies indicate that Cu(6bpyNO)Cl2 should be useful in organic spintronic applications.

  3. The effect of process parameters on the thermal conditions during moving mold ESR

    SciTech Connect

    Heilman, J.E.; Damkroger, B.K.

    1994-09-01

    Several experimental melts were conducted using a moving mold electroslag remelting furnace. The conditions of electrode immersion depth, slag cap thickness, and melt current were varied. Mold wall temperatures and slag pool temperatures were measured and the heat flux through the mold wall was calculated. The relationships between varying ESR melt parameters and the resultant thermal conditions were examined. The thermal profile of the mold, the heat transfer to the mold coolant total and fractional, and the formation of a slag skin were studied.

  4. Atom probe tomography study of internal interfaces in Cu2ZnSnSe4 thin-films

    NASA Astrophysics Data System (ADS)

    Schwarz, T.; Cojocaru-Mirédin, O.; Choi, P.; Mousel, M.; Redinger, A.; Siebentritt, S.; Raabe, D.

    2015-09-01

    We report on atom probe tomography studies of the composition at internal interfaces in Cu2ZnSnSe4 thin-films. For Cu2ZnSnSe4 precursors, which are deposited at 320 °C under Zn-rich conditions, grain boundaries are found to be enriched with Cu irrespective of whether Cu-poor or Cu-rich growth conditions are chosen. Cu2ZnSnSe4 grains are found to be Cu-poor and excess Cu atoms are found to be accumulated at grain boundaries. In addition, nanometer-sized ZnSe grains are detected at or near grain boundaries. The compositions at grain boundaries show different trends after annealing at 500 °C. Grain boundaries in the annealed absorber films, which are free of impurities, are Cu-, Sn-, and Se-depleted and Zn-enriched. This is attributed to dissolution of ZnSe at the Cu-enriched grain boundaries during annealing. Furthermore, some of the grain boundaries of the absorbers are enriched with Na and K atoms, stemming from the soda-lime glass substrate. Such grain boundaries show no or only small changes in composition of the matrix elements. Na and K impurities are also partly segregated at some of the Cu2ZnSnSe4/ZnSe interfaces in the absorber, whereas for the precursors, only Na was detected at such phase boundaries possibly due to a higher diffusivity of Na compared to K. Possible effects of the detected compositional fluctuations on cell performance are discussed.

  5. Molecular diffusion in porous media by PGSE ESR.

    PubMed

    Talmon, Yael; Shtirberg, Lazar; Harneit, Wolfgang; Rogozhnikova, Olga Yu; Tormyshev, Victor; Blank, Aharon

    2010-06-21

    Diffusion in porous media is a general subject that involves many fields of research, such as chemistry (e.g. porous catalytic pallets), biology (e.g. porous cellular organelles), and materials science (e.g. porous polymer matrixes for controlled-release and gas-storage materials). Pulsed-gradient spin-echo nuclear magnetic resonance (PGSE NMR) is a powerful technique that is often employed to characterize complex diffusion patterns inside porous media. Typically it measures the motion of at least approximately 10(15) molecules occurring in the milliseconds-to-seconds time scale, which can be used to characterize diffusion in porous media with features of approximately 2-3 mum and above (in common aqueous environments). Electron Spin Resonance (ESR), which operates in the nanoseconds-to-microseconds time scale with much better spin sensitivity, can in principle be employed to measure complex diffusion patterns in porous media with much finer features (down to approximately 10 nm). However, up to now, severe technical constraints precluded the adaptation of PGSE ESR to porous media research. In this work we demonstrate for the first time the use of PGSE ESR in the characterization of molecular restricted diffusion in common liquid solutions embedded in a model system for porous media made of sub-micron glass spheres. A unique ESR resonator, efficient gradient coils and fast gradient current drivers enable these measurements. This work can be further extended in the future to many applications that involve dynamical processes occurring in porous media with features in the deep sub-micron range down to true nanometric length scales. PMID:20372729

  6. ESR detection procedure of irradiated papaya containing high water content

    NASA Astrophysics Data System (ADS)

    Kikuchi, Masahiro; Shimoyama, Yuhei; Ukai, Mitsuko; Kobayashi, Yasuhiko

    2011-05-01

    ESR signals were recorded from irradiated papaya at liquid nitrogen temperature (77 K), and freeze-dried irradiated papaya at room temperature (295 K). Two side peaks from the flesh at the liquid nitrogen temperature indicated a linear dose response for 3-14 days after the γ-irradiation. The line shapes recorded from the freeze-dried specimens were sharper than those at liquid nitrogen temperature.

  7. The effect of Cu(2+) chelation on the direct photolysis of oxytetracycline: A study assisted by spectroscopy analysis and DFT calculation.

    PubMed

    Jin, Xin; Qiu, Shanshan; Wu, Ke; Jia, Mingyun; Wang, Fang; Gu, Chenggang; Zhang, Aiqian; Jiang, Xin

    2016-07-01

    The extensive usage of OTC and Cu(2+) in livestock and poultry industry caused high residues in natural environment. Co-contamination of OTC and Cu(2+) was a considerable environmental problem in surface waters. In this study, Cu(2+) mediated direct photolysis of OTC was studied. Cu(2+) chelating with OTC was found to greatly inhibit OTC photodegradation. To reveal the chelation mechanism of OTC-Cu complexes, multiple methods including UV-Vis absorption spectra, Infrared (IR) spectra, mass spectroscopy, and density functional theoretical (DFT) modeling were performed. Four OTC-Cu complexes were proposed. Cu(2+) preferably bond to O11O12 site with the binding constants logK = 8.19 and 7.86 for CuHL+ and CuL±, respectively. The second chelating site was suggested to be O2O3 with the binding constants of logK = 4.41 and 4.62 for Cu2HL3+ and Cu2L2+, respectively. The suppressed quantum yield of OTC by Cu2+ chelation was accused for their intra-/inter-molecular electron transfer, by which the energy in activated states was distributed. The occurrence of electron transfer between BCD ring and A ring also from BCD ring to Cu was evidenced by the TD-DFT result only for the OTC-Cu complexes. Besides, the cyclic voltammetry measurement also suggested one OTC-Cu(II)/OTC-Cu(I) redox couple. These results suggested that the persistence of OTC in environmental surface waters will probably be underestimated for neglecting the chelating effect of Cu2+. The photolysis quantum yield of OTC-Cu complexes, as well as the specific molar absorption constants, the equilibrium binding constants of Cu2+ with OTC could contribute to more accurate kinetic models of OTC. PMID:27155101

  8. Atom probe tomography studies on the Cu(In,ga)Se2 grain boundaries.

    PubMed

    Cojocaru-Mirédin, Oana; Schwarz, Torsten; Choi, Pyuck-Pa; Herbig, Michael; Wuerz, Roland; Raabe, Dierk

    2013-01-01

    Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the nanoscale and in three dimensions. Indeed, APT possesses high sensitivity (in the order of ppm) and high spatial resolution (sub nm). Considerable efforts were done here to prepare an APT tip which contains the desired grain boundary with a known structure. Indeed, site-specific sample preparation using combined focused-ion-beam, electron backscatter diffraction, and transmission electron microscopy is presented in this work. This method allows selected grain boundaries with a known structure and location in Cu(In,Ga)Se2 thin-films to be studied by atom probe tomography. Finally, we discuss the advantages and drawbacks of using the atom probe tomography technique to study the grain boundaries in Cu(In,Ga)Se2 thin-film solar cells. PMID:23629452

  9. Atom Probe Tomography Studies on the Cu(In,Ga)Se2 Grain Boundaries

    PubMed Central

    Cojocaru-Mirédin, Oana; Schwarz, Torsten; Choi, Pyuck-Pa; Herbig, Michael; Wuerz, Roland; Raabe, Dierk

    2013-01-01

    Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the nanoscale and in three dimensions. Indeed, APT possesses high sensitivity (in the order of ppm) and high spatial resolution (sub nm). Considerable efforts were done here to prepare an APT tip which contains the desired grain boundary with a known structure. Indeed, site-specific sample preparation using combined focused-ion-beam, electron backscatter diffraction, and transmission electron microscopy is presented in this work. This method allows selected grain boundaries with a known structure and location in Cu(In,Ga)Se2 thin-films to be studied by atom probe tomography. Finally, we discuss the advantages and drawbacks of using the atom probe tomography technique to study the grain boundaries in Cu(In,Ga)Se2 thin-film solar cells. PMID:23629452

  10. Study of Zn-Cu Ferrite Nanoparticles for LPG Sensing

    PubMed Central

    Jain, Anuj; Baranwal, Ravi Kant; Bharti, Ajaya; Vakil, Z.; Prajapati, C. S.

    2013-01-01

    Nanostructured zinc-copper mixed ferrite was synthesized using sol-gel method. XRD patterns of different compositions of zinc-copper ferrite, Zn(1−x)CuxFe2O4 (x = 0.0, 0.25, 0.50, 0.75), revealed single phase inverse spinel ferrite in all the samples synthesized. With increasing copper concentration, the crystallite size was found to be increased from 28 nm to 47 nm. The surface morphology of all the samples studied by the Scanning Electron Microscopy there exhibits porous structure of particles throughout the samples. The pellets of the samples are prepared for LPG sensing characteristics. The sensing is carried out at different operating temperatures (200, 225, and 250°C) with the variation of LPG concentrations (0.2, 0.4, and 0.6 vol%). The maximum sensitivity of 55.33% is observed at 250°C operating for the 0.6 vol% LPG. PMID:23864833

  11. ESR detection of wheat flour before and after irradiation

    NASA Astrophysics Data System (ADS)

    Shimoyama, Yuhei; Ukai, Mitsuko; Nakamura, Hideo

    2006-03-01

    We revealed free radicals in wheat flour before and after γ-ray irradiation and their thermal behavior during heat-treatment using electron spin resonance (ESR) spectroscopy. The ESR spectrum of wheat flour before irradiation consists of a sextet centered at g = 2.0 and a singlet signal at the same g-value position. The first one is attributable to a signal with hyperfine (hf) interactions of Mn 2+ ion (hf constant: 7.4 mT). The second is originated from carbon-centered radical. Upon γ-ray irradiation, however, a new signal with two triplet lines at the low and high field ends was detected in wheat flour on top of the Mn 2+ sextet lines. We analyzed the triplet ESR lines as powder spectra (rhombic g-tensor symmetry) with nitrogen ( 14N) hyperfine interactions. This indicates that a new organic radical was induced in the conjugated protein portion of wheat flour by the γ-ray irradiation. Intensity of the organic free radical at g = 2.0 detected in irradiated wheat flour increased monotonically by the thermal treatment. The analysis of the time-dependent evolution and decay process based on the theory of transient phenomena as well as the nonlinear least-squares numerical method provided a unique time constant for the radical evolution and decay in wheat flour during the heat-treatment.

  12. Direct ESR dating of a Pliocene hominin from Swartkrans.

    PubMed

    Curnoe, D; Grün, R; Taylor, L; Thackeray, F

    2001-05-01

    Two fragments of a hominin tooth (Australopithecus robustus) and two bovid teeth from the Hanging Remnant of the Swartkrans Formation were analysed with ESR. Research was complicated by the fact that the samples came from a curated collection and their precise provenance is unknown. The environmental dose rate was reconstructed by a series of in situ gamma spectrometric measurements and elemental analyses of a range of sediment samples. U-series isotopic analyses indicated that each of the teeth had a significantly different uranium uptake history, rendering the assumptive early U-uptake and linear U-uptake models ineffective. ESR and U-series data were combined to calculate open system ages, resulting in a best estimate of 1630+/-160 ka for the Hanging Remnant. An open-system model which provides the maximum age for given U-series and ESR measurements yielded an estimate of about 2100 ka. Two bovid teeth from Member 2, previously estimated to be between 1.0 and 2.0 Ma, yielded age estimates of between about 100 and 200 ka. No known geochemical processes are likely to explain this severe age underestimation. We conclude that these samples are of Middle to Upper Pleistocene age and their presence in Member 2 was either due to reworking or inadequate stratigraphical discrimination of these deposits. PMID:11322800

  13. Reported Early Family Environment Covaries with Menarcheal Age as a Function of Polymorphic Variation in Estrogen Receptor-α (ESR1)

    PubMed Central

    Manuck, Stephen B.; Craig, Anna E.; Flory, Janine D.; Halder, Indrani; Ferrell, Robert E.

    2010-01-01

    Age at menarche, a sentinel index of pubertal maturation, was examined in relation to early family relationships (conflict, cohesion) and polymorphic variation in the gene encoding estrogen receptor-α (ESR1) in a midlife sample of 455 European American women. Consistent with prior literature, women who reported being raised in families characterized by close interpersonal relationships and little conflict tended to reach menarche at a later age than participants reared in families lacking cohesion and prone to discord. Moreover, this association was moderated by ESR1 variation, such that quality of the family environment covaried positively with menarcheal age among participants homozygous for minor alleles of the two ESR1 polymorphisms studied here (rs9304799, rs2234693), but not among women of other ESR1 genotypes. In addition, a) family relationship variables were unrelated to ESR1 variation, and b) genotype-dependent effects of childhood environment on age at menarche could not be accounted for by personality traits elsewhere shown to explain heritable variation in reported family conflict and cohesion. These findings are consistent with theories of differential susceptibility to environmental influence, as well as the more specific hypothesis (by Belsky) that girls differ genetically in their sensitivity to rearing effects on pubertal maturation. PMID:21262040

  14. Genetically-induced Estrogen Receptor Alpha mRNA (Esr1) Overexpression Does Not Adversely Affect Fertility or Penile Development in Male Mice

    PubMed Central

    Heath, John; Abdelmageed, Yazeed; Braden, Tim D.; Williams, Carol S.; Williams, John W.; Paulose, Tessie; Hernandez-Ochoa, Isabel; Gupta, Rupesh; Flaws, Jodi A.; Goyal, Hari O.

    2011-01-01

    Previously, we reported that estrogen receptor alpha mRNA (Esr1) or protein (ESR1) overexpression resulting from neonatal exposure to estrogens in rats was associated with infertility and mal-developed penis characterized by reduced length and weight and abnormal accumulation of fat cells. The objective of this study was to determine if mutant male mice overexpressing Esr1 are naturally infertile or have reduced fertility and/or develop abnormal penis. The fertility parameters, including fertility and fecundity indices, numbers of days from the day of cohabitation to the day of delivery, and numbers of pups per female, were not altered from controls, as a result of Esr1 overexpression. Likewise, penile morphology, including the length, weight, and diameter and os penis development, was not altered from controls. Conversely, weights of the seminal vesicles and bulbospongiosus and levator ani (BS/LA) muscles were significantly (P < 0.05) lower as compared to controls; however, the weight of the testis, the morphology of the testis and epididymis, and the plasma and testicular testosterone concentration were not different from controls. Hence, the genetically-induced Esr1 overexpression alone, without an exogenous estrogen exposure during the neonatal period, is unable to adversely affect the development of the penis as well as other male reproductive organs, except limited, but significant, reductions in weights of the seminal vesicles and BS/LA muscles. PMID:20930192

  15. Polymorphisms in the LPL and CETP Genes and Haplotype in the ESR1 Gene Are Associated with Metabolic Syndrome in Women from Southwestern Mexico

    PubMed Central

    Cahua-Pablo, José Ángel; Cruz, Miguel; Méndez-Palacios, Abigail; Antúnez-Ortiz, Diana Lizzete; Vences-Velázquez, Amalia; del Carmen Alarcón-Romero, Luz; Parra, Esteban Juan; Tello-Flores, Vianet Argelia; Leyva-Vázquez, Marco Antonio; Valladares-Salgado, Adán; Pérez-Macedonio, Claudia Paola; Flores-Alfaro, Eugenia

    2015-01-01

    Metabolic syndrome (MetS) is a combination of metabolic disorders associated with an increased risk for cardiovascular disease (CVD). Studies in women reported associations between polymorphisms in ESR1, LPL and CETP genes and MetS. Our aim was to evaluate the association between variants in ESR1, LPL and CETP genes with MetS and its components. Four hundred and eighty women were analyzed, anthropometric features and biochemical profiles were evaluated, and genotyping was performed by real-time PCR. We found an association with elevated glucose levels (odds ratio (OR) = 2.9; p = 0.013) in carrying the AA genotype of rs1884051 in the ESR1 gene compared with the GG genotype, and the CC genotype of rs328 in the LPL gene was associated with MetS compared to the CG or GG genotype (OR = 2.8; p = 0.04). Moreover, the GA genotype of rs708272 in the CETP gene is associated with MetS compared to the GG or AA genotype (OR = 1.8; p = 0.006). In addition the ACTCCG haplotype in the ESR1 gene is associated with a decrease in the risk of MetS (OR = 0.02; p < 0.001). In conclusion, our results show the involvement of the variants of ESR1, LPL and CETP genes in metabolic events related to MetS or some of its features. PMID:26370976

  16. Generation of Esr1-Knockout Rats Using Zinc Finger Nuclease-Mediated Genome Editing

    PubMed Central

    Dhakal, Pramod; Kubota, Kaiyu; Chakraborty, Damayanti; Lei, Tianhua; Larson, Melissa A.; Wolfe, Michael W.; Roby, Katherine F.; Vivian, Jay L.

    2014-01-01

    Estrogens play pivotal roles in development and function of many organ systems, including the reproductive system. We have generated estrogen receptor 1 (Esr1)-knockout rats using zinc finger nuclease (ZFN) genome targeting. mRNAs encoding ZFNs targeted to exon 3 of Esr1 were microinjected into single-cell rat embryos and transferred to pseudopregnant recipients. Of 17 live births, 5 had biallelic and 1 had monoallelic Esr1 mutations. A founder with monoallelic mutations was backcrossed to a wild-type rat. Offspring possessed only wild-type Esr1 alleles or wild-type alleles and Esr1 alleles containing either 482 bp (Δ482) or 223 bp (Δ223) deletions, indicating mosaicism in the founder. These heterozygous mutants were bred for colony expansion, generation of homozygous mutants, and phenotypic characterization. The Δ482 Esr1 allele yielded altered transcript processing, including the absence of exon 3, aberrant splicing of exon 2 and 4, and a frameshift that generated premature stop codons located immediately after the codon for Thr157. ESR1 protein was not detected in homozygous Δ482 mutant uteri. ESR1 disruption affected sexually dimorphic postnatal growth patterns and serum levels of gonadotropins and sex steroid hormones. Both male and female Esr1-null rats were infertile. Esr1-null males had small testes with distended and dysplastic seminiferous tubules, whereas Esr1-null females possessed large polycystic ovaries, thread-like uteri, and poorly developed mammary glands. In addition, uteri of Esr1-null rats did not effectively respond to 17β-estradiol treatment, further demonstrating that the Δ482 Esr1 mutation created a null allele. This rat model provides a new experimental tool for investigating the pathophysiology of estrogen action. PMID:24506075

  17. Matrix isolation ESR spectroscopy and magnetic anisotropy of D{sub 3h} symmetric septet trinitrenes

    SciTech Connect

    Misochko, Eugenii Ya.; Akimov, Alexander V.; Masitov, Artem A.; Korchagin, Denis V.; Aldoshin, Sergei M.; Chapyshev, Sergei V.

    2013-05-28

    The fine-structure (FS) parameters D of a series of D{sub 3h} symmetric septet trinitrenes were analyzed theoretically using density functional theory (DFT) calculations and compared with the experimental D values derived from ESR spectra. ESR studies show that D{sub 3h} symmetric septet 1,3,5-trichloro-2,4,6-trinitrenobenzene with D=-0.0957 cm{sup -1} and E= 0 cm{sup -1} is the major paramagnetic product of the photolysis of 1,3,5-triazido-2,4,6-trichlorobenzene in solid argon matrices at 15 K. Trinitrenes of this type display in the powder X-band ESR spectra intense Z{sub 1}-transition at very low magnetic fields, the position of which allows one to precisely calculate the parameter D of such molecules. Thus, our revision of the FS parameters of well-known 1,3,5-tricyano-2,4,6-trinitrenobenzene [E. Wasserman, K. Schueller, and W. A. Yager, Chem. Phys. Lett. 2, 259 (1968)] shows that this trinitrene has Double-Vertical-Line D Double-Vertical-Line = 0.092 cm{sup -1} and E= 0 cm{sup -1}. DFT calculations reveal that, unlike C{sub 2v} symmetric septet trinitrenes, D{sub 3h} symmetric trinitrenes have the same orientations of the spin-spin coupling tensor D-caret{sub SS} and the spin-orbit coupling tensor D-caret{sub SOC} and, as a result, have negative signs for both the D{sub SS} and D{sub SOC} values. The negative magnetic anisotropy of septet 2,4,6-trinitrenobenzenes is considerably strengthened on introduction of heavy atoms in the molecules, owing to an increase in contributions of various excitation states to the D{sub SOC} term.

  18. The ESR1 gene is associated with risk for canine mammary tumours

    PubMed Central

    2013-01-01

    Background The limited within-breed genetic heterogeneity and an enrichment of disease-predisposing alleles have made the dog a very suitable model for the identification of genes associated with risk for specific diseases. Canine mammary cancer is an example of such a disease. However, the underlying inherited risk factors for canine mammary tumours (CMTs) are still largely unknown. In this study, 52 single nucleotide polymorphisms (SNPs) in ten human cancer-associated genes were genotyped in two different datasets in order to identify genes/alleles associated with the development of CMTs. The first dataset consisted of English Springer Spaniel (ESS) CMT cases and controls. ESS is a dog breed known to be at increased risk of developing CMTs. In the second dataset, dogs from breeds known to have a high frequency of CMTs were compared to dogs from breeds with a lower occurrence of these tumours. Results We found significant associations to CMT for SNPs and haplotypes in the estrogen receptor 1 (ESR1) gene in the ESS material (best PBonf = 0.021). A large number of SNPs, among them several SNPs in ESR1, showed significantly different allele frequencies between the high and low risk breed groups (best PBonf = 8.8E-32, best PBPerm = 0.076). Conclusions The identification of CMT-associated SNPs in ESR1 in two independent datasets suggests that this gene might be involved in CMT development. These findings also support that CMT may serve as a good model for human breast cancer research. PMID:23574728

  19. Local translational diffusion rates of membranous Na+,K(+)-ATPase measured by saturation transfer ESR spectroscopy.

    PubMed Central

    Esmann, M; Marsh, D

    1992-01-01

    Diffusion-controlled Heisenberg spin exchange between spin-labeled Na+,K(+)-ATPase [ATP phosphohydrolase (Na+/K(+)-transporting), EC 3.6.1.37] proteins has been studied by saturation transfer ESR spectroscopy in reconstituted membranes. Na+,K(+)-ATPase from the salt gland of Squalus acanthias was solubilized in a polyoxyethylene ether detergent, octa(ethylene glycol) dodecyl monoether. Part of the solubilized enzyme was covalently spin-labeled with a nitroxide derivative of indanedione and recombined with various proportions of the unlabeled enzyme while the native lipid/protein ratio was maintained. Purified membranes were then reconstituted from the various samples by precipitation with divalent ions. The reciprocal integrated intensities of the saturation transfer ESR spectra were found to increase linearly with the fraction of protein that was spin-labeled, and the gradient of the concentration dependence increased with increasing temperature over the range 4 degrees-25 degrees C. Comparison with theoretical analyses of the effects of weak Heisenberg spin exchange [Marsh, D. & Horváth, L. I. (1992) J. Magn. Reson. 97, 13-26] suggests that the effects on the saturation transfer ESR intensity are attributable to short-range diffusional collisions between the spin-labeled protein molecules. The effective value of the local translational diffusion coefficient is 1.8-2.9 microns2.s-1 at 15 degrees C, depending on the diffusion model used, which is much larger than the values obtained for the long-range diffusion coefficient in cells by photobleaching techniques. The temperature dependence of the translational diffusion is larger than expected but correlates with the anomalous temperature dependence of the rotational diffusion observed in the same system. PMID:1323847

  20. Variable temperature EPR studies of Cu2+ and VO2+ doped potassium dihydrogen citrate (C6H7KO7)

    NASA Astrophysics Data System (ADS)

    Aygun, Zeynep

    2013-03-01

    Electron paramagnetic resonance (EPR) studies of single crystals and powder samples of Cu2+ and VO2+ doped potassium dihydrogen citrate (PDHC) have been carried out at different temperatures. The temperature-dependant g and A values have been obtained for powder spectra of both Cu2+ and VO2+ ions in PDHC and the ground state of Cu2+ ion has been determined. The powder spectra recorded for Cu2+ ion in the temperature range 70-298 K are discussed with Jahn-Teller distortion. It is concluded that the g and A values of Cu2+: PDHC show the static property at low temperatures. For all temperatures, the result g// < g⊥ < ge of VO2+: PDHC indicates that the unpaired electron exists in the dxy orbital.

  1. Studies of impurity occupation and local angular distortions for Cu2+ in CdS films at different concentrations

    NASA Astrophysics Data System (ADS)

    Li, Guo-Liang; Wu, Shao-Yi; Zhang, Li-Juan; Xu, Yong-Qiang; Zhang, Zhi-Hong

    2016-02-01

    In order to clarify impurity occupation and local structures for Cu2+ in the CdS films, the g factors and hyperfine structure constants (HSCs) and their concentration dependences are theoretically studied from the perturbation calculations for both the cases of tetragonally compressed tetrahedral (TCT) and tetragonally elongated octahedral (TEO) 3d9 clusters. Despite similar g anisotropies g // > g ⊥ > 2, the calculated g factors and HSCs and their concentration dependences based on the TCT [CuS4]6- cluster show much better agreement with the experimental data than those based on the previously assigned TEO [CuS6]10- cluster. So, the g factors and HSCs can be ascribed to the substitutional TCT [CuS4]6- cluster on Cd2+ site, and the possibility of the previous assignment of interstitial TEO [CuS6]10- cluster may be tentatively excluded. In the TCT [CuS4]6- clusters, the local Cu2+-S2- bond angles θ related to C4 axis are found to be about 1.54° larger than the ideal value θ 0 (≈54.736°) of a regular tetrahedron owing to the Jahn-Teller effect. The magnitudes of g factors and HSCs demonstrate the overall increasing trends with increasing Cu2+ concentration, attributable to the decrease of covalency (increase of covalency factor N) and the increases of the angular deviation Δθ (=θ - θ 0) and the core polarization constant κ.

  2. A comparative study on shock compression of nanocrystalline Al and Cu: Shock profiles and microscopic views of plasticity

    SciTech Connect

    Ma, Wen; Hou, Yong; Zhu, Wenjun

    2013-10-28

    Shock compressions of nanocrystalline (nc) metals Al and Cu with the same grain size and texture are studied by using molecular dynamics simulations. Results have revealed that the shock front of both Al and Cu can be divided into three stages: elastic, grain-boundary-mediated, and dislocation-mediated plastic deformation. The transition planes among these three stages are proven to be non-planar by two-dimensional shock response analysis, including local stress, shear, temperature, and atom configuration. The difference between shocked Al and Cu is that the rise rate of the elastic stage of Cu is slightly higher than that of Al, and that the shock-front width of Al is wider than Cu at the same loading conditions. For the plastic stage, the dislocation density of shocked Al is lower than Cu, and the contribution of grain-boundary-mediated plasticity to shock front and strain for nc Al is more pronounced than for nc Cu. These results are explained through intrinsic material properties and atomistic analysis of the plastic process. In the case of the shocked Al sample, partial dislocations, perfect dislocations, and twins are observed, but few evidence of perfect dislocations and twins are observed in the shocked Cu.

  3. NMR and specific heat study of atomic dynamics and spin-orbit behavior in Cu2-xAgyTe

    NASA Astrophysics Data System (ADS)

    Sirusi, Ali A.; Ballikaya, Sedat; Chen, Jing-Han; Uher, Ctirad; Ross, Joseph H., Jr.

    We report studies of Cu2Te and Cu2-xAgyTe, promising candidates for thermoelectric and photovoltaic applications. Cu and Te NMR show that above a well-defined 200 K onset, Cu2Te exhibits Cu-ion hopping, leading to the higher-temperature superionic motion. In Cu1.98Ag0.2Te the onset increases to 250 K. In the low-temperature static phase the properties are nearly identical. Aside from Korringa terms there are large diamagnetic contributions for all nuclei, comparable to those for other systems with very large spin-orbit and/or inverted band configurations. Thus the system may be a topologically interesting system like the similar phase Ag2Te. Results will be compared to DFT calculations of NMR shifts. The low-temperature spectra also indicate two distinct local environments for Cu sites, one corresponding to high symmetry such as characterizes the high-temperature cubic phase, and one with much more asymmetry. In addition, specific heat results are consistent with about 50% of the Cu ions being weakly bound on Einstein-oscillator sites. We tentatively connect these results to reported local inhomogeneity due to vacancy condensation in similar systems.

  4. Electrochemical and spectroscopic study of novel Cu and Fe-based catalysts for oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    He, Qinggang; Yang, Xiaofang; He, Ruihua; Bueno-López, Agustín; Miller, Hamish; Ren, Xiaoming; Yang, Wanli; Koel, Bruce E.

    2012-09-01

    We synthesized two “single-core” Fe-Nx/C and Cu-Nx/C electrocatalysts and a bi-core CuFe-Nx/C composite electrocatalyst using iron and copper phthalocyanine-based precursors and a high-temperature pyrolysis method. The morphology, structure, and activity toward the oxygen reduction reaction (ORR) in alkaline media were evaluated for each electrocatalyst by transmission electron microscopy (TEM), X-ray Diffraction (XRD), and the rotating ring-disk electrode (RRDE) method. Although the Cu-Nx/C catalyst showed lower catalytic activity than Fe-Nx/C, the presence of Cu enhanced the ORR performance of bi-core CuFe-Nx/C, as compared to single-core Fe-Nx/C. To fully understand the synergistic effect between Cu and Fe on this enhancement, high resolution X-ray photoelectron spectroscopy (HR-XPS) and soft X-ray absorption spectroscopy (XAS) was employed to study the electronic structure of as-synthesized electrocatalysts. The HR-XPS analysis showed that metal-nitrogen bonding was maintained and that the oxidation states of Fe and Cu were influenced by the presence of the second metal in the bi-core catalyst. The XAS data revealed that a fraction of an electron was transferred from Fe to Cu, which may help to lower the kinetic barrier during the ORR process. Based on our experimental results and four different models, we briefly discuss ORR mechanisms on these metallic catalysts.

  5. EPR and optical absorption studies of Cu2+ doped lithium maleate dihydrate single crystal

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Pandey, Shri Devi

    Electron paramagnetic resonance (EPR) study of Cu2+ doped lithium maleate dihydrate single crystal is done at liquid nitrogen temperature (LNT). Four hyperfine lines are observed in all directions, i.e. only a single site is observed. The spin Hamiltonian parameters are determined from EPR spectra: gx=2.100±0.002, gy=2.162±0.002, gz=2.215±0.002, Ax=(55±5)×10-4 cm-1, Ay=(52±5)×10-4 cm-1, Az=(50±5)×10-4 cm-1. The results indicate that the copper ion enters the lattice interstitially. Using the spin Hamiltonian parameters obtained from EPR study the ground state wave function of Cu2+ ion in the lattice is determined. The optical absorption study of Cu2+ doped lithium maleate dihydrate at room temperature is also performed. With the help of optical and EPR data, the nature of bonding in the complex is discussed.

  6. Supercritical hydrothermal synthesis of Cu{sub 2}O(SeO{sub 3}): Structural characterization, thermal, spectroscopic and magnetic studies

    SciTech Connect

    Larranaga, Aitor

    2009-01-08

    Cu{sub 2}O(SeO{sub 3}) has been synthesized in supercritical hydrothermal conditions, using an externally heated steel reactor with coupled hydraulic pump for the application of high pressure. The compound crystallizes in the P2{sub 1}3 cubic space group. The unit cell parameter is a = 9.930(1) A with Z = 12. The crystal structure has been refined by the Rietveld method. The limit of thermal stability is, approximately, 490 deg. C. Above this temperature the compound decomposes to SeO{sub 2}(g) and CuO(s). The IR spectrum shows the characteristic bands of the (SeO{sub 3}){sup 2-} oxoanion. In the diffuse reflectance spectrum two intense absorptions characteristic of the Cu(II) cations in five-coordination are observed. The ESR spectra are isotropic from room temperature to 5 K, with g = 2.11(2). The thermal evolution of the intensity and line width of the signals suggest a ferromagnetic transition in the 50-45 K range. Magnetic measurements, at low temperatures, confirm the existence of a ferromagnetic transition with a critical temperature of 55 K.

  7. Characterization and biological studies on Co(II), Ni(II) and Cu(II) complexes of carbohydrazones ending by pyridyl ring

    NASA Astrophysics Data System (ADS)

    Abu El-Reash, G. M.; El-Gammal, O. A.; Ghazy, S. E.; Radwan, A. H.

    2013-03-01

    The chelating behavior of ligands based on carbohydrazone core modified with pyridine end towards Co(II), Ni(II) and Cu(II) ions have been examined. The ligands derived from the condensation of carbohydrazide with 2-acetylpyridine (H2APC) and 4-acetylpyridine (H2APEC). The 1H NMR, IR data and the binding energy calculations of H2APC revealed the presence of two stereoisomers syn and anti in the solid state and in the solution. The 1H NMR, IR data and the binding energy calculations confirmed the presence of H2APEC in one keto form only in the solid state and in the solution. The spectroscopic data confirmed that H2APC behaves as a monobasic pentadentate in Co(II) and Cu(II) complexes and as mononegative tetradentate in Ni(II) complex. On the other hand, H2APEC acts as a mononegative tridentate in Co(II) complex, neutral tridentate in Ni(II) complex and neutral bidentate in Cu(II) complex. The electronic spectra and the magnetic measurements of complexes as well as the ESR of the copper complexes suggested the octahedral geometry. The bond length and bond angles were evaluated by DFT method using material studio program. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The antioxidant (DDPH and ABTS methods), anti-hemolytic and in vitro Ehrlich ascites of the compounds have been screened.

  8. Binding of Cu(II) ions to peptides studied by fluorescence spectroscopy and isothermal titration calorimetry.

    PubMed

    Makowska, Joanna; Żamojć, Krzysztof; Wyrzykowski, Dariusz; Uber, Dorota; Wierzbicka, Małgorzata; Wiczk, Wiesław; Chmurzyński, Lech

    2016-01-15

    Steady-state and time-resolved fluorescence quenching measurements supported by Isothermal Titration Calorimetry (ITC) were used to study the interactions of Cu(2+) with four peptides. Two of them were taken from the N-terminal part of the FBP28 protein (formin binding protein) WW domain: Tyr-Lys-Thr-Ala-Asp-Gly-Lys-Thr-Tyr-NH2 (D9) and its mutant Tyr-Lys-Thr-Ala-Asn-Gly-Lys-Thr-Tyr-NH2 (D9_M) as well as two mutated peptides from the B3 domain of the immunoglobulin binding protein G derived from Streptococcus: Asp-Val-Ala-Thr-Tyr-Thr-NH2 (J1) and Glu-Val-Ala-Thr-Tyr-Thr-NH2 (J2). The measurements were carried out at 298.15K in 20mM 2-(N-morpholino)ethanesulfonic acid (MES) buffer solution with a pH of 6. The fluorescence of all peptides was quenched by Cu(2+) ions. The stoichiometry, conditional stability constants and thermodynamic parameters for the interactions of the Cu(2+) ions with D9 and D9_M were determined from the calorimetric data. The values of the conditional stability constants were additionally determined from fluorescence quenching measurements and compared with those obtained from calorimetric studies. There was a good correlation between data obtained from the two techniques. On the other hand, the studies revealed that J1 and J2 do not exhibit an affinity towards metal ions. The obtained results prove that fluorescence quenching experiments may be successfully used in order to determine stability constants of complexes with fluorescent ligands. Finally, based on the obtained results, the coordinating properties of the peptides towards the Cu(2+) ions are discussed. PMID:26363471

  9. Binding of Cu(II) ions to peptides studied by fluorescence spectroscopy and isothermal titration calorimetry

    NASA Astrophysics Data System (ADS)

    Makowska, Joanna; Żamojć, Krzysztof; Wyrzykowski, Dariusz; Uber, Dorota; Wierzbicka, Małgorzata; Wiczk, Wiesław; Chmurzyński, Lech

    2016-01-01

    Steady-state and time-resolved fluorescence quenching measurements supported by Isothermal Titration Calorimetry (ITC) were used to study the interactions of Cu2 + with four peptides. Two of them were taken from the N-terminal part of the FBP28 protein (formin binding protein) WW domain: Tyr-Lys-Thr-Ala-Asp-Gly-Lys-Thr-Tyr-NH2 (D9) and its mutant Tyr-Lys-Thr-Ala-Asn-Gly-Lys-Thr-Tyr-NH2 (D9_M) as well as two mutated peptides from the B3 domain of the immunoglobulin binding protein G derived from Streptococcus: Asp-Val-Ala-Thr-Tyr-Thr-NH2 (J1) and Glu-Val-Ala-Thr-Tyr-Thr-NH2 (J2). The measurements were carried out at 298.15 K in 20 mM 2-(N-morpholino)ethanesulfonic acid (MES) buffer solution with a pH of 6. The fluorescence of all peptides was quenched by Cu2 + ions. The stoichiometry, conditional stability constants and thermodynamic parameters for the interactions of the Cu2 + ions with D9 and D9_M were determined from the calorimetric data. The values of the conditional stability constants were additionally determined from fluorescence quenching measurements and compared with those obtained from calorimetric studies. There was a good correlation between data obtained from the two techniques. On the other hand, the studies revealed that J1 and J2 do not exhibit an affinity towards metal ions. The obtained results prove that fluorescence quenching experiments may be successfully used in order to determine stability constants of complexes with fluorescent ligands. Finally, based on the obtained results, the coordinating properties of the peptides towards the Cu2 + ions are discussed.

  10. Estrogen receptor 1 (ESR1; ERα), not ESR2 (ERβ), modulates estrogen-induced sex reversal in the American alligator, a species with temperature-dependent sex determination.

    PubMed

    Kohno, Satomi; Bernhard, Melissa C; Katsu, Yoshinao; Zhu, Jianguo; Bryan, Teresa A; Doheny, Brenna M; Iguchi, Taisen; Guillette, Louis J

    2015-05-01

    All crocodilians and many turtles exhibit temperature-dependent sex determination where the temperature of the incubated egg, during a thermo-sensitive period (TSP), determines the sex of the offspring. Estrogens play a critical role in sex determination in crocodilians and turtles, as it likely does in most nonmammalian vertebrates. Indeed, administration of estrogens during the TSP induces male to female sex reversal at a male-producing temperature (MPT). However, it is not clear how estrogens override the influence of temperature during sex determination in these species. Most vertebrates have 2 forms of nuclear estrogen receptor (ESR): ESR1 (ERα) and ESR2 (ERβ). However, there is no direct evidence concerning which ESR is involved in sex determination, because a specific agonist or antagonist for each ESR has not been tested in nonmammalian species. We identified specific pharmaceutical agonists for each ESR using an in vitro transactivation assay employing American alligator ESR1 and ESR2; these were 4,4',4''-(4-propyl-[1H]-pyrazole-1,3,5-triyl)trisphenol (PPT) and 7-bromo-2-(4-hydroxyphenyl)-1,3-benzoxazol-5-ol (WAY 200070), respectively. Alligator eggs were exposed to PPT or WAY 200070 at a MPT just before the TSP, and their sex was examined at the last stage of embryonic development. Estradiol-17β and PPT, but not WAY 200070, induced sex reversal at a MPT. PPT-exposed embryos exposed to the highest dose (5.0 μg/g egg weight) exhibited enlargement and advanced differentiation of the Müllerian duct. These results indicate that ESR1 is likely the principal ESR involved in sex reversal as well as embryonic Müllerian duct survival and growth in American alligators. PMID:25714813

  11. [Study on Contents and Budgets of Cu, Zn and Cd in an Arable Soil Using AAS].

    PubMed

    Zhao, Ying; Jiang, Chun-ming; Ma, Qiang; Zhou, Hua; Xu, Yong-gang; Yu, Wan-tai

    2015-12-01

    Based on a long-term experiment in Shenyang Experimental Station, the effect of manure application on the contents and budgets of Cu, Zn and Cd in the arable soil was studied. The experiment included four treatments: no mature addition (CK), mature addition 10 t · ha⁻¹ year⁻¹(M1), 25 t · ha⁻¹ year⁻¹ (M2), and 50 t · ha⁻¹ year⁻¹(M3). The result showed that Cu, Zn and Cd in soil were accumulated with manure application and prolongation of experiment, and the accumulative magnitude increased with increasing of manure application. The average annual growth rates of the heavy metals in the four treatments (CK, M1, M2, M3) were 2.83%, 6.56%, 7.54%, 8.96%; 0.03%, 3.44%, 4.53%, 6.64% and 1.51%, 8.01%, 10. 27%, 16. 08% for Cu, Zn and Cd, respectively. After six years of the experiment, the content of Cd in the M3 treatment was quite close to the threshold of Chinese Soil Quality Standard Grade III (1 mg · kg⁻¹, GB15618-1995). After 12 years of the experiment, the contents of Cu in the mature-amended treatments fell in the Chinese Soil Quality Standard Grade III, which should be paid more attention. Although the heavy metals in soil were gradually accumulated, the Cu, Zn and Cd levels in crop grain were still below the National Food Contamination Standards (GB2762-2005; GB13106-91; GB15199-94), indicating the contents of heavy metals in crop produced from contaminated soil might not exceed the corresponding standards. The contents of Cu, Zn and Cd in the straw were much greater than those in the grain. The removal of heavy metal by crop was in the order of M3 > M2 > M1 > CK. The average amounts of Cu, Zn and Cd annually removed from the soil in the four treatments (CK, M1, M2 and M3) were 35.68, 47.80, 63.65, 69.64; 249.14, 375.22, 375.16, 444.44, and 0.83, 1.39, 1.64, 1.66 g · ha⁻¹, respectively. The contents of heavy metals in organic manure varied in different years: the contents of Cu and Zn increased year by year, while Cd presented a

  12. X-ray Photoelectron Diffraction (XPD) Study of the Growth of Cu on clean and O-precovered Ru(0001).

    NASA Astrophysics Data System (ADS)

    Ruebush, S. R.; Couch, R. E.; Fadley, C. S.; Thevuthasan, S.

    1996-03-01

    We have studied the growth of Cu on clean and O-precovered Ru(0001) for the first time with XPD, measuring experimental O 1s (E_kin=958 eV), Cu 2p3/2 (E_kin=554 eV), and Ru 3d (E_kin=1206eV) intensities over nearly the full 2π solid angle above the surface for Cu coverages from submonolayer up to many monolayers. We have analyzed our data using single and multiple scattering diffraction calculations. We have found a continuous Cu interlayer spacing from 1.84 Åat 1 ML to about 2.00 Åat 8 ML, with the bulk Cu spacing being 2.08 ÅWe have also studied the effect that a surfactant such as oxygen has on the growth of Cu. Our XPD studies show that all oxygen floats on the Cu surface. In addition, a preliminary analysis of our data suggests a tendency towards island growth for about 1-3 ML. We will compare our results with prior theoretical and experimental studies of this system.

  13. Study of structural and optical properties of Fe doped CuO nanoparticles

    NASA Astrophysics Data System (ADS)

    Rani, Poonam; Gupta, Ankita; Kaur, Sarabjeet; Singh, Vishal; Kumar, Sacheen; Kumar, Dinesh

    2016-05-01

    Iron doped Copper oxide nanoparticles were synthesized by the co-precipitation method at different concentration (3%, 6%, 9%) at 300-400° C with Copper Acetate and Ferric Chloride as precursors in presence of Polyethylene Glycol and Sodium Hydroxide as stabilizing agent. Effect of doping on the structural and optical properties is studied. The obtained nanoparticles were characterized by X-Ray Diffraction and UV-Visible Spectroscopy for examining the size and the band gap respectively. The X-Ray Diffraction plots confirmed the monoclinic structure of Copper oxide suggesting the Cu atoms replaced by Fe atoms and no secondary phase was detected. The indirect band gap of Fe doped CuO nanoparticles is 2.4eV and increases to 3.4eV as the concentration of dopant increases. The majority of particle size is in range 8 nm to 35.55 nm investigated by X-ray diffractometer.

  14. Ab initio study of heterojunction discontinuities in the ZnO/Cu2O system

    NASA Astrophysics Data System (ADS)

    Zemzemi, M.; Alaya, S.; Ben Ayadi, Z.

    2014-06-01

    Solar cells based on transparent conductive oxides such as ZnO/Cu2O constitute a very advanced way to build high-performance cells. In this work, we are interested in the characterization of the interface through nanoscale modeling based on ab initio approaches (density functional theory, local density approximation, and pseudopotential). This work aims to build a supercell containing a heterojunction ZnO/Cu2O and study the structural properties and the discontinuity of the valence band (band offset) from a semiconducting to another phase. We build a zinc oxide in the wurtzite structure along [0001] on which we place the copper oxide in the hexagonal (CdI2-type) structure. We choose the method of Van de Walle and Martin to calculate the energy offset. This approach fits well the density functional theory. Our calculation of the band offset gives a value that corresponds to other experimental and theoretical values.

  15. The Guanine Cation Radical: Investigation of Deprotonation States by ESR and DFT

    PubMed Central

    Adhikary, Amitava; Kumar, Anil; Becker, David; Sevilla, Michael D.

    2008-01-01

    This work reports ESR studies that identify the favored site of deprotonation of the guanine cation radical (G•+) in an aqueous medium at 77 K. Using ESR and UV-visible spectroscopy, one-electron oxidized guanine is investigated in frozen aqueous D2O solutions of 2′-deoxyguanosine (dGuo) at low temperatures at various pHs at which the guanine cation, G•+ (pH 3–5), singly deprotonated species, G(-H)• (pH 7–9) and doubly deprotonated species, G(-2H)•− (pH>11) are found. C-8-deuteration of dGuo to give 8-D-dGuo removes the major proton hyperfine coupling at C-8. This isolates the anisotropic nitrogen couplings for each of the three species and aids our analyses. These anisotropic nitrogen couplings were assigned to specific nitrogen sites by use of 15N substituted derivatives at N1, N2 N3 atoms in dGuo. Both ESR and UV-visible spectra are reported for each of the species: G•+, G(-H)•, and G(-2H)•−. The experimental anisotropic ESR hyperfine couplings are compared to those obtained from DFT calculations for the various tautomers of G(-H)•. Using the B3LYP/6–31G(d) method, the geometries and energies of G•+ and its singly deprotonated state in its two tautomeric forms, G(N1-H)• and G(N2-H)•, were investigated. In a non-hydrated state G(N2-H)• is found to be more stable than G(N1-H)• but on hydration with 7 water molecules G(N1-H)• is found to be more stable than G(N2-H)•. The theoretically calculated hyperfine coupling constants (HFCC) of G•+, G(N1-H)• and G(-2H)•− match the experimentally observed HFCCs best on hydration with 7 or more waters. For G(-2H)•−, the hyperfine coupling constant (HFCC) at the exocyclic nitrogen atom (N2) is especially sensitive to the number of hydrating water molecules; good agreement with experiment is not obtained until 9 or 10 waters of hydration are included. PMID:17125389

  16. Synthesis, characterization and crystal structure of some bidentate heterocyclic Schiff base ligands of 4-toluoyl pyrazolones and its mononuclear Cu(II) complexes

    NASA Astrophysics Data System (ADS)

    Vyas, Komal M.; Jadeja, R. N.; Gupta, Vivek K.; Surati, K. R.

    2011-03-01

    We depict the synthesis of a new set of six bidentate heterocyclic Schiff base ligands, formed by the condensation of three different 4-toluoyl pyrazolones with various aromatic amines in ethanolic medium. All of these ligands have been characterized on the basis of elemental analysis, IR, 1H NMR, 13C NMR and Mass spectral data. The molecular geometries of three of these ligands have been determined by single crystal X-ray study. It reveals that these ligands exist in amine-one tautomeric form in the solid state. The reaction of these ligands with copper(II) resulted in the formation of mononuclear complexes having the general composition [CuL 2(H 2O) 2] with two water molecules at axial positions. These complexes have been characterized on the basis of elemental analysis, Cu-estimation, molar conductivity, magnetic measurements, IR, UV-Visible, FAB-Mass, TG-DTA-DSC data, cyclic voltametric measurements and ESR spectral studies. ESR spectra and magnetic susceptibility measurements indicates distorted octahedral stereochemistry of Cu(II) complexes, while non-electrolytic behaviour of complexes indicates the absence of counter ion.

  17. Polarized Rayleigh and Raman Study of single CuO Nanowire

    NASA Astrophysics Data System (ADS)

    Lu, Qiujie; Wu, Jian; Gutierrez, Humberto; Russin, Timothy; Eklund, Peter

    2009-03-01

    Crystalline CuO is an interesting Ferroelectric and Ferromagnetic system which we have recently grown in nanowire (NW) form. In this paper, we present results of Raman and Rayleigh scattering studies of individual CuO NWs to probe optical antenna effects that we first discovered in GaP NWs. We have shown that these antenna effects can, in general, strongly mask Raman selection rules in semiconducting nanowires[1]. Using a microRaman spectrometer, polarized light scattering experiments (backscattering geometry) were carried on NWs suspended over holes in a TEM grid. TEM was therefore also used to identify the growth axis and determine the NW diameter. As a function of the angle q between the NW axis and the incident laser field, we collect the Rayleigh scattering intensity as well as the Raman LO and TO optical phonon scattering intensity. These results can then be used to quantify the optical antenna effects in the CuO system. NWs of different diameters, from 70nm to 200 nm were studied; the results depend dramatically on the NW diameter. Our results will be compared to EM calculations based on the DDA approximation. This work is supported by NSF NIRT, grant DMR-0304178. [1] Chen G. Jian Wu, etc., Nano Lett. 2008 Vol.8 pp. 1341-1346.

  18. Comparative Density Functional Study of Methanol Decomposition on Cu4 and Co4 Clusters

    SciTech Connect

    Mehmood, Faisal; Greeley, Jeffrey P.; Zapol, Peter; Curtiss, Larry A.

    2010-11-18

    A density functional theory study of the decomposition of methanol on Cu4 and Co4 clusters is presented. The reaction intermediates and activation barriers have been determined for reaction steps to form H2 and CO. For both clusters, methanol decomposition initiated by C-H and O-H bond breaking was investigated. In the case of a Cu4 cluster, methanol dehydrogenation through hydroxymethyl (CH2OH), hydroxymethylene (CHOH), formyl (CHO), and carbon monoxide (CO) is found to be slightly more favorable. For a Co4 cluster, the dehydrogenation pathway through methoxy (CH3O) and formaldehyde (CH2O) is slightly more favorable. Each of these pathways results in formation of CO and H2. The Co cluster pathway is very favorable thermodynamically and kinetically for dehydrogenation. However, since CO binds strongly, it is likely to poison methanol decomposition to H2 and CO at low temperatures. In contrast, for the Cu cluster, CO poisoning is not likely to be a problem since it does not bind strongly, but the dehydrogenation steps are not energetically favorable. Pathways involving C-O bond cleavage are even less energetically favorable. The results are compared to our previous study of methanol decomposition on Pd4 and Pd8 clusters. Finally, all reaction energy changes and transition state energies, including those for the Pd clusters, are related in a linear, Broensted-Evans-Polanyi plot.

  19. A high temperature diffraction-resistance study of chalcopyrite, CuFeS{sub 2}

    SciTech Connect

    Engin, T.E.; Powell, A.V.; Hull, S.

    2011-08-15

    The electrical, magnetic and structural properties of synthetic chalcopyrite, CuFeS{sub 2}, have been studied up to 873 K using DC resistance measurements performed in-situ during neutron powder diffraction experiments. Under ambient conditions the material adopts the accepted structural model for CuFeS{sub 2} in the space group I4-bar 2d, with the magnetic moment of the Fe{sup 3+} cations aligned along [001]. The electrical resistivity is around 0.3 {Omega} cm under ambient conditions, consistent with semiconductor character, and decreases slightly with increase in temperature until a more abrupt fall occurs in the region 750-800 K. This abrupt change in resistivity is accompanied by a structural transition to a cubic zinc blende structured phase (space group F4-bar 3m) in which Cu{sup +} and Fe{sup 3+} cations are disordered over the same tetrahedral crystallographic sites and by a simultaneous loss of long-range magnetic order. The implications of these results are discussed in the context of previous studies of the chalcopyrite system. - Graphical abstract: Structural, magnetic and electrical properties of CuFeS{sub 2} to 873 K have been investigated using DC resistance measurements, performed in-situ during the collection of powder neutron diffraction data. Highlights: > Structural, magnetic and electronic properties are probed simultaneously. > A fall in resistivity at high temperatures is associated with cation disorder. > The order-disorder transition is accompanied by the loss of magnetic order. > The structural and magnetic phase transition is preceded by a 2-phase region. > Sulphur loss at high temperatures causes the phase transitions to be irreversible.

  20. Measurement of the Effective Susceptibility at the Surface of YBa2Cu3O7-δ Superconductor

    NASA Astrophysics Data System (ADS)

    Darabont, Al.; Giurgiu, L. V.; Pop, A. V.

    The intra- and intergranular superconducting correlations in YBa2Cu3O7-δ are characterized by the ac susceptibility measurements. The effective susceptibility is measured as a function of temperature by the Electron-Spin-Resonance (ESR) method, using two DPPH paramagnetic markers placed on the surface of a cylindrical superconducting sample. The appearance of two separate ESR lines at Tc confirms the values of critical transition temperatures determined by the ac susceptibility.

  1. First-principles study of the organometallic S =1/2 kagome compound Cu(1,3-bdc)

    NASA Astrophysics Data System (ADS)

    Liu, Zheng; Mei, Jia-Wei; Liu, Feng

    2015-10-01

    Cu(1,3-benzenedicarboxylate) [Cu(1,3-bdc)] contains structurally perfect kagome planes formed by Cu2 + ions without the presence of diamagnetic defects. This organometallic compound should serve as a precious platform to explore quantum frustrated magnetism, yet the experimental results so far are mysterious, leading to questions such as, "Is Cu(1,3-bdc) just a trivial weak ferromagnet?" Using the density functional theory, we have systematically studied the electronic and magnetic properties of Cu(1,3-bdc), putting forth a theoretical basis to clarify this novel material. We present numerical evidence of a dominating antiferromagnetic (AFM) exchange between nearest-neighbor (NN) Cu2 + as experimentally extracted from the high-temperature susceptibility data. We further show that beyond the NN AFM exchange, the additional interactions in Cu(1,3-bdc) have similar strength as those in the well-studied kagome antiferromagnet, herbertsmithite, by designing a comparative study. In the end, we discuss our understanding of the phase transition and FM signals observed under low temperature.

  2. Studies on formation mechanism of 3D Cu2O nanospheres through self-assembly of 0D nanodots

    NASA Astrophysics Data System (ADS)

    Zhang, Lun; Yu, Bing; Ying, Pengzhan; Wu, Ling; Chen, Shanliang; Wang, Jieru; Gu, Xiuquan; Zhou, Rui; Ni, Zhonghai

    2015-08-01

    Cu2O crystals with different morphologies (solid and porous) and sizes (from 25 to 282 nm) were synthesized controllably through a facile solvothermal route. The growth mechanism was investigated by SEM and TEM with varying the concentration of poly (vinylpyrrolidone) (PVP, K30), CH3COO- (Ac-) and NO3- acid ions in the precursor solution. The self-assembly of three types of Cu2O nano-structures was observed through a general route of zero-dimensional (0D) → 2D → 3D. When Cu(Ac)2ṡH2O was used as the copper sources, 0D Cu2O nanodots with size of 2-7 nm were firstly assembled to 2D quasi-spherical and bookmark-like structures via Oriented attachment (OA), and then converted into 3D hierarchical Cu2O nanoclusters (a few tens of nm) and porous sub-microspheres with an average size of 282 nm, respectively. While Cu(NO3)2ṡ3H2O was used instead of Cu(Ac)2ṡH2O, the similar assembly process occurred leading to the formation of Cu2O porous nanospheres of 40-140 nm which exhibit better adsorption ability toward methyl orange compared with activated carbon. In addition, we also investigated the dependence of Cu2O crystals on the concentration of acid ions (Ac- and NO3-). Compared with Ac-, the size and morphology of the obtained products were less dependent on the concentration of NO3- acid ions. This study might provide a new insight into the growth mechanism of Cu2O based micro- or nanostructures.

  3. Association of ESR1 gene tagging SNPs with breast cancer risk

    PubMed Central

    Dunning, Alison M.; Healey, Catherine S.; Baynes, Caroline; Maia, Ana-Teresa; Scollen, Serena; Vega, Ana; Rodríguez, Raquel; Barbosa-Morais, Nuno L.; Ponder, Bruce A.J.; Low, Yen-Ling; Bingham, Sheila; Haiman, Christopher A.; Le Marchand, Loic; Broeks, Annegien; Schmidt, Marjanka K.; Hopper, John; Southey, Melissa; Beckmann, Matthias W.; Fasching, Peter A.; Peto, Julian; Johnson, Nichola; Bojesen, Stig E.; Nordestgaard, Børge; Milne, Roger L.; Benitez, Javier; Hamann, Ute; Ko, Yon; Schmutzler, Rita K.; Burwinkel, Barbara; Schürmann, Peter; Dörk, Thilo; Heikkinen, Tuomas; Nevanlinna, Heli; Lindblom, Annika; Margolin, Sara; Mannermaa, Arto; Kosma, Veli-Matti; Chen, Xiaoqing; Spurdle, Amanda; Change-Claude, Jenny; Flesch-Janys, Dieter; Couch, Fergus J.; Olson, Janet E.; Severi, Gianluca; Baglietto, Laura; Børresen-Dale, Anne-Lise; Kristensen, Vessela; Hunter, David J.; Hankinson, Susan E.; Devilee, Peter; Vreeswijk, Maaike; Lissowska, Jolanta; Brinton, Louise; Liu, Jianjun; Hall, Per; Kang, Daehee; Yoo, Keun-Young; Shen, Chen-Yang; Yu, Jyh-Cherng; Anton-Culver, Hoda; Ziogoas, Argyrios; Sigurdson, Alice; Struewing, Jeff; Easton, Douglas F.; Garcia-Closas, Montserrat; Humphreys, Manjeet K.; Morrison, Jonathan; Pharoah, Paul D.P.; Pooley, Karen A.; Chenevix-Trench, Georgia

    2009-01-01

    We have conducted a three-stage, comprehensive single nucleotide polymorphism (SNP)-tagging association study of ESR1 gene variants (SNPs) in more than 55 000 breast cancer cases and controls from studies within the Breast Cancer Association Consortium (BCAC). No large risks or highly significant associations were revealed. SNP rs3020314, tagging a region of ESR1 intron 4, is associated with an increase in breast cancer susceptibility with a dominant mode of action in European populations. Carriers of the c-allele have an odds ratio (OR) of 1.05 [95% Confidence Intervals (CI) 1.02–1.09] relative to t-allele homozygotes, P = 0.004. There is significant heterogeneity between studies, P = 0.002. The increased risk appears largely confined to oestrogen receptor-positive tumour risk. The region tagged by SNP rs3020314 contains sequence that is more highly conserved across mammalian species than the rest of intron 4, and it may subtly alter the ratio of two mRNA splice forms. PMID:19126777

  4. Synthesis and microstructural studies of annealed Cu(2)O/Cu(x)S bilayer as transparent electrode material for photovoltaic and energy storage devices.

    PubMed

    Taleatu, B A; Arbab, E A A; Omotoso, E; Mola, G T

    2014-10-01

    Cu2 O thin film and a transparent bilayer have been fabricated by electrodeposition method. The growths were obtained in potentiostatic mode with gradual degradation of anodic current. X-ray diffraction (XRD) study showed that the bilayer is polycrystalline and it possesses mixture of different crystallite phases of copper oxides. Surface morphology of the films was investigated by scanning electron microscopy (SEM). The SEM images revealed that the films were uniformly distributed and the starting material (Cu2 O) had cubical structure. Grains agglomeration and crystallinity were enhanced by annealing. Optical studies indicated that all the samples have direct allowed transition. Energy band gap of the bilayer film was reduced by annealing treatment thus corroborating quantum confinement upshot. PMID:25088932

  5. Thermodynamic study of CuO/Cu2O and Co3O4/CoO redox pairs for solar energy thermochemical storage

    NASA Astrophysics Data System (ADS)

    Alonso, Elisa; Gallo, Alessandro; Pérez-Rábago, Carlos; Fuentealba, Edward

    2016-05-01

    Thermochemical storage of solar energy consists in reversible chemical reactions that absorb the solar heat during an endothermic step and release it by means of an exothermic reaction. CuO/Cu2O and Co3O4/CoO redox pairs have a high potential as materials to store solar energy at high temperature. Cobalt oxides have been so far studied by several authors and works while copper oxides suitability has been recently proved. However, in both cases, operation parameters need to be optimized. A theoretical study of the effect of total pressure, gas/solid molar rate and composition of working atmosphere on the systems equilibrium is presented. The equilibrium displacement caused by these parameters is calculated and discussed. Finally, some ideas for tentative implementations of these systems are commented.

  6. EPR study of Cu2+ ion doped orotato(nicotinamid)cobalt(II) single crystal

    NASA Astrophysics Data System (ADS)

    Yıldırım, İ.; Karabulut, B.; Büyükgüngör, O.

    2016-01-01

    We have studied the Cu2+ ion doped orotato(nicotinamid)cobalt(II) complex by using EPR spectroscopy and X-ray diffraction. The single crystal is triclinic with the space group P 1 ‾ . The unit cell dimensions of the crystal are a = 7.2785(4) Å, b = 10.2349(5) Å, c = 12.7372(6) Å, α = 69.297(4)°, β = 74.791(4)° and γ = 76.995(4)°, with Z = 2. We analyzed the EPR spectra of both single crystal and powder of the complex at room temperature. EPR analysis indicates the presence of only one Cu2+ site. We obtained the spin Hamiltonian parameters from the single crystal data for the complex. The spin Hamiltonian parameters are gx = 2.032, gy = 2.116, gz = 2.319, Ax = 28 G, Ay = 66 G, Az = 126 G. These data indicate that the symmetry of paramagnetic center is rhombic. We constructed the ground state wave function of the Cu2+ ion.

  7. Study of the properties of CuInSe{sub 2} materials prepared from nanoparticle powder

    SciTech Connect

    Mehdaoui, S. Benslim, N.; Aissaoui, O.; Benabdeslem, M.; Bechiri, L.; Otmani, A.; Portier, X.; Nouet, G.

    2009-05-15

    This work studies the properties of CuInSe{sub 2} (CIS) thin films obtained from nanoparticle powder. The samples were prepared by direct thermal evaporation of ball milled powder from a tungsten crucible onto precleaned glass substrates, using a BALZERS coating unit. The as deposited films were annealed in a vacuum at different temperatures. The composition, structure, morphology and optical properties of these samples have been investigated. X-ray diffraction (XRD) results showed that the CuInSe{sub 2} phase may be prepared by mechanical alloying method. The crystallites of the CIS powder were found to be partially copper-rich. The as-deposited film was polycrystalline in nature having chalcopyrite structure as a mainly phase. The surface morphology is homogeneous across the surface. Expected optical properties (E{sub g} = 1.04 eV, {alpha} {approx} 10{sup 4} cm{sup -1}) and near stoichiometric composition (Cu: 23.62 at.%, In: 24.35 at.% and Se: 52.03 at.%) were determined.

  8. EPR study of Cu(2+) ion doped orotato(nicotinamid)cobalt(II) single crystal.

    PubMed

    Yıldırım, I; Karabulut, B; Büyükgüngör, O

    2016-01-01

    We have studied the Cu(2+) ion doped orotato(nicotinamid)cobalt(II) complex by using EPR spectroscopy and X-ray diffraction. The single crystal is triclinic with the space group P1‾. The unit cell dimensions of the crystal are a=7.2785(4)Å, b=10.2349(5)Å, c=12.7372(6)Å, α=69.297(4)°, β=74.791(4)° and γ=76.995(4)°, with Z=2. We analyzed the EPR spectra of both single crystal and powder of the complex at room temperature. EPR analysis indicates the presence of only one Cu(2+) site. We obtained the spin Hamiltonian parameters from the single crystal data for the complex. The spin Hamiltonian parameters are gx=2.032, gy=2.116, gz=2.319, Ax=28G, Ay=66G, Az=126G. These data indicate that the symmetry of paramagnetic center is rhombic. We constructed the ground state wave function of the Cu(2+) ion. PMID:25704568

  9. Synthesis and characterization studies of MgO:CuO nanocrystals by wet-chemical method

    NASA Astrophysics Data System (ADS)

    Kaviyarasu, K.; Maria Magdalane, C.; Anand, K.; Manikandan, E.; Maaza, M.

    2015-05-01

    In this report, we examine the progress in adapting these nanomaterials for several predominantly photonics device fabrication by wet-chemical method. Nanocomposite of magnesium oxide (MgO) with copper oxide (CuO) doped nanoparticles were characterized by X-ray powder diffraction (XRD) and the observed peaks are quite agreeable with the pure phase cubic structure. High-resolution transmission electron microscopic (HR-TEM) results reveal that the resultant nanopowders are porous and agglomerated with polycrystalline nano-entities. Field emission of selected-area electron diffraction (SAED) studies showed that the average size of the nanoparticles were 20 nm. Photoluminescence spectra of MgO:CuO were investigated, showing emission peaks around 375 nm relating to new energy levels induced by defects or defect levels generation and confocal micro-Raman images indicated that the chemical molecular vibrational band structure and morphology of the product which is spherical shaped nanoparticles with an average particle size of ∼25 nm with standard deviation. The electrochemical response of MgO:CuO which is proves that the nano-copper/magnesium has high functionality due to the small size and it has higher electrochemical activity without any modifications.

  10. Preparation and neutron diffraction study of polycrystalline Cu-Zn-Fe materials

    NASA Astrophysics Data System (ADS)

    Darul, J.; Nowicki, W.

    2009-10-01

    Polycrystalline oxides Cu1-xZnxFe2O4 (0.0≤x≤0.05) have been successfully prepared by a simple combustion method using citrate-nitrate precursors. The nature of structural transition in inverse spinels and ferrimagnetic behavior of the materials have been investigated by the neutron diffraction technique. At room temperature neutron diffraction study confirms the presence of a single-phase structure, where tetragonal unit cell with c/a>1 is observed. In these distorted spinel ferrites it is found that tetragonal → cubic transformation is attributed to the decrease of the concentration of Jahn-Teller ions Cu2+ (d9) in the host structure at the octahedral sites as a result of zinc substitution. The introduction of non-magnetic ion in place of Cu2+ in the spinel unit cell results in the reduction of intersublattice contributions, this in turn decreases temperature of the magnetic ordering (Curie point) in these diluted ferrimagnets.

  11. Magnetic studies of CuFe2O4 nanoparticles prepared by co-precipitation method

    NASA Astrophysics Data System (ADS)

    Subha, A.; Shalini, M. Govindaraj; Sahoo, Subasa C.

    2016-05-01

    Cu-ferrite nanoparticles were synthesized by co-precipitation method and were annealed at different temperatures ranging from 400 to l000°C in air for 4 hours. The as-prepared sample and the sample annealed at 400°C showed small peaks of cubic Cu-ferrite in X-ray diffraction studies. For the intermediate temperature 600°C, some additional peaks of α-Fe2O3 were observed. As the annealing temperature increased further only tetragonal Cu-ferrite peaks were observed. In all the samples some traces of CuO was noted. Grain size was increased from 2lnm for the as prepared sample to 42nm for the sample annealed at l000°C. Spontaneous magnetization value was found to be very small for the as prepared sample and it was increased monotonically with the increase in annealing temperature. Maximum magnetization of 29.7emu/g was observed at 300K for the sample annealed at l000°C. The remanent magnetization was increased with the increase in annealing temperature up to 900°C and then decreased whereas for the coercivity a peak was observed for the sample annealed at 800°C. The highest coercivity of l402 Oe was observed at 300K for the sample annealed at 800°C. As the measurement temperature decreased from 300K to 60K, magnetization and coercivity values were increased. The observed magnetic behaviour may be understood on the basis of phase transformation, grain growth with the increase in annealing temperature and reduced thermal energy at low measurement temperature.

  12. Reactive oxygen species scavenging activity of Jixueteng evaluated by electron spin resonance (ESR) and photon emission.

    PubMed

    Toyama, Toshizo; Wada-Takahashi, Satoko; Takamichi, Maomi; Watanabe, Kiyoko; Yoshida, Ayaka; Yoshino, Fumihiko; Miyamoto, Chihiro; Maehata, Yojiro; Sugiyama, Shuta; Takahashi, Shun-Suke; Todoki, Kazuo; Lee, Masaichi-Chang-Il; Hamada, Nobushiro

    2014-12-01

    Jixueteng, the dried stem of Spatholobus suberectus Dunn (Leguminosae), is a traditional Chinese herbal medicine that is commonly classified as a herb that promotes blood circulation and can be used to treat blood stasis. The aim of this study was to examine the reactive oxygen species (ROS) scavenging activity of Jixueteng and other herbal medicines. The ROS scavenging activities of the water extracts of Jixueteng, Cnidium officinale and Salvia miltiorrhiza were examined using an electron spin resonance (ESR) technique and faint luminescence measurement. The ESR signal intensities of the superoxide anion (O2·) and hydroxyl radical (HO·) were reduced more by Jixueteng than the other herbal medicines we tested. High photon emission intensity to hydrogen peroxide (H202) and HO· was observed in Jixueteng using the XYZ chemiluminescence system that was used as faint luminescence measurement and analysis. The results of the present study revealed that the ROS scavenging activity of 8% Jixueteng was the strongest among the herbal medicines we tested. It has been reported that Jixueteng includes various polyphenols. In the ROS scavenging activity by Jixueteng, it is supposed that the antioxidant activity caused by these polyphenols would contribute greatly. In conclusion, a water extract component of Jixueteng had potent free radical scavenging activity and an antioxidative effect that inhibited the oxidative actions of O2·⁻, H2O2 and HO·. Therefore, Jixueteng represents a promising therapeutic drug for reactive oxygen-associated pathologies. PMID:25632478

  13. Magnetic excitations in the spin-1/2 triangular-lattice antiferromagnet Cs2CuBr4

    SciTech Connect

    Zvyagin, S. A.; Ozerov, M.; Kamenskyi, D.; Wosnitza, J.; Krzystek, J.; Yoshizawa, D.; Hagiwara, M.; Hu, Rongwei; Ryu, Hyejin; Petrovic, C.; Zhitomirsky, M. E.

    2015-11-27

    We present on high- field electron spin resonance (ESR) studies of magnetic excitations in the spin- 1/2 triangular-lattice antiferromagnet Cs2CuBr4. Frequency- field diagrams of ESR excitations are measured for different orientations of magnetic fields up to 25 T. We show that the substantial zero- field energy gap, Δ ≈ 9.5 K, observed in the low-temperature excitation spectrum of Cs2CuBr4 [Zvyagin et al:, Phys. Rev. Lett. 112, 077206 (2014)], is present well above TN. Noticeably, the transition into the long-range magnetically ordered phase does not significantly affect the size of the gap, suggesting that even below TN the high-energy spin dynamics in Cs2CuBr4 is determined by short-range-order spin correlations. The experimental data are compared with results of model spin-wave-theory calculations for spin-1/2 triangle-lattice antiferromagnet.

  14. ESR1 gene promoter region methylation in free circulating DNA and its correlation with estrogen receptor protein expression in tumor tissue in breast cancer patients

    PubMed Central

    2014-01-01

    Background Tumor expression of estrogen receptor (ER) is an important marker of prognosis, and is predictive of response to endocrine therapy in breast cancer. Several studies have observed that epigenetic events, such methylation of cytosines and deacetylation of histones, are involved in the complex mechanisms that regulate promoter transcription. However, the exact interplay of these factors in transcription activity is not well understood. In this study, we explored the relationship between ER expression status in tumor tissue samples and the methylation of the 5′ CpG promoter region of the estrogen receptor gene (ESR1) isolated from free circulating DNA (fcDNA) in plasma samples from breast cancer patients. Methods Patients (n = 110) with non-metastatic breast cancer had analyses performed of ER expression (luminal phenotype in tumor tissue, by immunohistochemistry method), and the ESR1-DNA methylation status (fcDNA in plasma, by quantitative methylation specific PCR technique). Results Our results showed a significant association between presence of methylated ESR1 in patients with breast cancer and ER negative status in the tumor tissue (p = 0.0179). There was a trend towards a higher probability of ESR1-methylation in those phenotypes with poor prognosis i.e. 80% of triple negative patients, 60% of HER2 patients, compared to 28% and 5.9% of patients with better prognosis such as luminal A and luminal B, respectively. Conclusion Silencing, by methylation, of the promoter region of the ESR1 affects the expression of the estrogen receptor protein in tumors of breast cancer patients; high methylation of ESR1-DNA is associated with estrogen receptor negative status which, in turn, may be implicated in the patient’s resistance to hormonal treatment in breast cancer. As such, epigenetic markers in plasma may be of interest as new targets for anticancer therapy, especially with respect to endocrine treatment. PMID:24495356

  15. Analysis of anisotropic spin-label motion in saturation-transfer ESR spectra of spin-labeled cowpea chlorotic mottle virus

    NASA Astrophysics Data System (ADS)

    Hemminga, M. A.; Faber, A. J.

    A saturation-transfer ESR study is carried out on maleimide spin-labeled cowpea chlorotic mottle virus dissolved in various glycerol-water systems. The saturation-transfer ESR spectra were analyzed by comparing them with reference spectra of isotropically reorienting spin labels. The results are interpreted in terms of the overall motion of the virus particle, described by an isotropic rotational correlation time τR, and a local anisotropic spin-label motion with rotational correlation times τ| and τ⊥.

  16. Electrical properties of Cu/a-BaTiO3/Cu capacitors studied in dc and ac regimes

    NASA Astrophysics Data System (ADS)

    El Kamel, F.; Gonon, P.; Radnóczi, G.

    2009-04-01

    Electrical properties of Cu/a-BaTiO3/Cu capacitors have been investigated in both dc and ac regimes as a function of temperature. A clear correlation is found between the temperature dependence of dc leakage currents and the temperature variation of the dielectric relaxation, showing that these measurement techniques are probing the same defects. Using either of these two techniques, we were able to detect at least three types of electrical active defects. Oxygen vacancy diffusion takes place at high temperature with an activation energy of around 1 eV. The diffusion of copper creates ionic defects in the a-BaTiO3 layer, which introduces two other contributions to the conduction process. The first is related to the motion of ionic species (ionic conduction, thermally activated with an activation energy of 0.3 eV). In addition, it has been argued that the presence of copper ions introduces a discrete set of shallow traps within the bandgap, resulting in a n-type conductivity (electronic conduction). The traps depth and their effective density are 0.45 eV and 4×1016 cm-3, respectively.

  17. Lack of association between the ESR1 rs9340799 polymorphism and age at menarche: a meta-analysis.

    PubMed

    Wu, H Y; Xing, X K; Wang, K J; Zhang, L

    2016-01-01

    It has been reported that the estrogen receptor alpha (ESR1) rs9340799 polymorphism is associated with age at menarche (AAM). However, recent investigations have generated inconsistent results. This study aimed to establish a more precise estimation of the association between this polymorphism and AAM. A meta-analysis was conducted based on an in silico literature search using PubMed. Six studies presenting continuous data, including ESR1 rs9340799 genotype frequencies, were selected. Effect size was estimated using Hedges' adjusted g with 95% confidence intervals (CIs), which were calculated based on the standardized mean difference between groups of subjects and different genotypes. No evidence of an association between the ESR1 rs9340799 polymorphism and AAM was found in the pooled continuous data under any genotype comparison (AA vs GG+AG: Hedges' g = -0.085, 95%CI = -0.202-0.032, P = 0.156; GG vs AA+AG: Hedges' g = 0.143, 95%CI = -0.041-0.327, P = 0.129; A vs G: Hedges' g = 0.187, 95%CI = -0.032-0.406, P = 0.095). Moreover, a funnel plot generated using this data was found to be symmetrical using the Egger (P = 0.797) and Begg tests (P = 0.851), indicating the absence of publication bias. In summary, our meta-analysis shows that the ESR1 rs9340799 polymorphism is not a significant, independent contributing factor to AAM. To validate this finding, further studies involving larger numbers of participants are needed. PMID:27525849

  18. Magnetic and dielectric studies of Li-Cu co-doped ZnO nanoparticles

    NASA Astrophysics Data System (ADS)

    Vivek, S.; Ajith, S. K.; Chitralekha, C. S.; Nair, Swapna S.

    2016-05-01

    Room temperature ferromagnetism has been observed in Li-Cu co-doped ZnO nanoparticles prepared by sol-gel route. Our studies indicated that the observed ferromagnetism is a surface phenomenon which depends on oxygen vacancy and the nature of the dopants. Dependence of ferromagnetism on the annealing temperature indicated the role of oxygen vacancy, and the decrease in coercivity as the particle size increases indicates the surface dependence of ferromagnetism. It is found that the addition of dopants also enhanced ferromagnetism. Dielectric studies indicated an increase in dielectric constant as the doping concentration is increased.

  19. First-principles study of transparent p-type conductive SrCu2O2 and related compounds

    NASA Astrophysics Data System (ADS)

    Nie, Xiliang; Wei, Su-Huai; Zhang, S. B.

    2002-02-01

    Using first-principles band structure methods we have systematically studied the electronic and optical properties of p-type transparent conductive oxides SrCu2O2 and related compounds AIICu2O2, where A=Mg, Ca, and Ba, as well as their host material Cu2O. We show that all these compounds have direct band gap at the zone center (Γ) with SrCu2O2 having the largest band gap. The trend of band gap variation of AIICu2O2 as a function of AII is explained in terms of atomic energy levels and atomic sizes of the AII elements. Transparency of SrCu2O2 is explained by the calculated dipole transition matrix elements. The calculated effective masses for the conduction band states are found to be larger than those for the valence states for SrCu2O2, opposite to the trend in conventional semiconductors and n-type transparent conductive oxides. We predict that adding a small amount of Ca (~16%) into SrCu2O2 can increase the band gap and reduce the hole effective mass of SrCu2O2, therefore, increase the transparency and conductivity.

  20. Multiscale Study of Interfacial Intermetallic Compounds in a Dissimilar Al 6082-T6/Cu Friction-Stir Weld

    NASA Astrophysics Data System (ADS)

    Avettand-Fenoël, M. N.; Taillard, R.; Ji, G.; Goran, D.

    2012-12-01

    The objective of this work was to characterize the Al x Cu y intermetallic compounds (IMCs) formed at the abutting interface during solid-state friction-stir welding (FSW) of 6082 aluminum alloy and pure copper. As IMCs are potential sources of flaws in case of mechanical loading of welds, their study is essential at various scale lengths. In the present case, they have been identified by neutron diffraction, electron backscattered diffraction, and transmission electron microscopy. Neutron diffraction analyses have shown that a shift of the tool from the interface, in particular towards the Cu part, generates an increase of the IMCs' volume fraction. In accordance with an exacerbation of its kinetics of formation by FSW, a 4- μm-thick layer has precipitated at the interface despite the shortness of the thermal cycle. This layer is composed of two sublayers with the Al4Cu9 and Al2Cu stoichiometry, respectively. Convergent beam electron diffraction analyses have, however, disclosed that the crystallography of the current Al2Cu compound does not comply with the usual tetragonal symmetry of this phase. The Al2Cu phase formation results from both the local chemical composition and thermodynamics, whereas the development of Al4Cu9 is rather due to both the local chemical composition and the shortness of the local FSW thermal cycle.

  1. Interaction of CO and NO with the spinel CuCr2O4 (100) surface: A DFT study

    NASA Astrophysics Data System (ADS)

    Xu, Xiang-Lan; Chen, Wen-Kai; Chen, Zhan-Hong; Li, Jun-Qian; Li, Yi

    The characteristics of CO and NO molecules at Cu2+ and Cr3+ ion sites on the CuCr2O4 (100) surface have been studied by first principles calculations based on spin-polarized density functional theory (DFT). The calculated results show that adsorption energies for X-down(C, N) adsorption vary in the order: Cu2+-CO>Cr3+-NO≈Cr3+-CO>Cu2+-NO. CO molecules are preferentially adsorbed at Cu sites, whereas NO molecules adsorb favorably at Cu2+ and Cr3+ ion sites. The C-O and N-O stretching frequencies are red-shifted upon adsorption. Combining the analysis of frontier molecular orbitals and Mulliken charge, for CO and NO X-down adsorption systems, the 5sigma orbitals donate electrons and the 2pi* orbitals obtain back-donated electrons. Although for NO with O-down adsorption systems, the NO-2pi* orbitals obtain back-donated electrons from substrates without 5sigma-donation. Coadsorption calculations show the CO/NO mixture adsorb selectively at the Cu2+ion site but simultaneously at the Cr3+ ion site, respectively.

  2. Adsorption and dissociation of O 2 on CuCl(1 1 1) surface: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Zhang, Riguang; Liu, Hongyan; Wang, Baojun; Ren, Jun; Li, Zhong

    2011-10-01

    The adsorption and dissociation of O 2 on CuCl(1 1 1) surface have been systematically studied by the density functional theory (DFT) slab calculations. Different kinds of possible modes of atomic O and molecular O 2 adsorbed on CuCl(1 1 1) surface and possible dissociation pathways are identified, and the optimized geometry, adsorption energy, vibrational frequency and Mulliken charge are obtained. The calculated results show that the favorable adsorption occurs at hollow site for O atom, and molecular O 2 lying flatly on the surface with one O atom binding with top Cu atom is the most stable adsorption configuration. The O-O stretching vibrational frequencies are significantly red-shifted, and the charges transferred from CuCl to oxygen. Upon O 2 adsorption, the oxygen species adsorbed on CuCl(1 1 1) surface mainly shows the characteristic of the superoxo (O 2-), which primarily contributes to improving the catalytic activity of CuCl, meanwhile, a small quantity of O 2 dissociation into atomic O also occur, which need to overcome very large activation barrier. Our results can provide some microscopic information for the catalytic mechanism of DMC synthesis over CuCl catalyst from oxidative carbonylation of methanol.

  3. A Comparable Study on Structural and Optical Properties of Cu2ZnSnS4 and Cu2ZnSnSe4 Nanocrystallines

    NASA Astrophysics Data System (ADS)

    Gu, Xiuquan; Zhang, Shuang; Zhao, Yulong; Zhu, Lei; Qiang, Yinghuai

    2014-10-01

    In this study, single-kesterite-phase Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) nanocrystallines have been synthesized by a simple solvothermal route. Scanning electron microscopy (SEM), X-ray diffraction (XRD), ultraviolet-visible (UV-vis) absorbance and Raman scattering spectroscopy were used to characterize the optical and micro-structure properties of the as-synthesized samples. The bandgap of CZTS could be tuned in a large range by incorporating a few Se atoms. Both the CZTS and CZTSe exhibited the similar temperature dependence of the Raman "A" modes, including a monotonic redshift in peak position and an irregular variation in peak linewidth. Such a behavior might be due to the cumulative effect of thermal expansion and small crystalline sizes.

  4. ESR Microscopy for Biological and Biomedical Applications

    PubMed Central

    Shin, C. S.; Dunnam, C. R.; Borbat, P. P.; Dzikovski, B.; Barth, E. D.; Halpern, H. J.; Freed, J. H.

    2011-01-01

    We report on electron-spin resonance microscopy (ESRM) providing sub-micron resolution (~700nm) with a high spin concentration sample, i.e. lithium phthalocyanine (LiPc) crystal. For biomedical applications of our ESRM, we have imaged samples containing rat basophilic leukemia (RBL) cells as well as cancerous tissue samples with a resolution of several microns using a water soluble spin probe, Trityl_OX063_d24. Phantom samples with the nitroxide spin label, 15N PDT, were also imaged to demonstrate that nitroxides, which are commonly used as spin labels, may also be used for ESRM applications. ESRM tissue imaging would therefore be valuable for diagnostic or therapeutic purposes. Also, ESRM can be used to study the motility or the metabolism of cells in various environments. With further modification and/or improvement of imaging probe and spectrometer instrumentation sub-micron biological images should be obtainable, thereby providing a useful tool for various biomedical applications. PMID:21984955

  5. E-layer dominated ionosphere observed by EISCAT/ESR radars during solar minimum

    NASA Astrophysics Data System (ADS)

    Cai, Hongtao; Li, Fei; Shen, Ge; Zhan, Weijia; Zhou, Kangjun; McCrea, Ian W.; Ma, Shuying

    2014-05-01

    E-layer dominated ionosphere (ELDI) is referred to vertical profiles having peak density at E-layer altitudes (Mayer and Jakowski, 2009). In this paper, characteristics of ELDI were investigated with the help of field-aligned measurements of EISCAT/ESR radars during 2009-2011. ELDI events were identified with simple but reasonable criterions, in which a minimal duration was required to exclude possible 'fake' events induced by random errors in measurements. It was found that ELDI were observed more often in winter than other seasons. In winter, occurrence of ELDI peaks around mid-night at auroral latitude, while it reaches its maximum around geomagnetic local noon at ESR latitude. Our results imply that ELDI looks like a sporadic rather than a regular phenomenon, being contrary to previous results inferred from radio occultation measurements. Discrepancy in duration of ELDI events observed by the two radars is remarkable, being 30 minutes at TromsØ on average and about a half of it at Svalbard. During the presence of ELDI, average thickness of E-layer exhibits undetectable variations at the two sites, as well as HmE and the ratio of NmE/NmF. Case studies reveal that either extra E-layer ionization possible induced by auroral precipitation or density depletion in F-layer caused by plasma convection alone could lead to the presence of ELDI. We suggest that both them play an important role in ELDI formation.

  6. Estimation of background radiation doses for the Peninsular Malaysia's population by ESR dosimetry of tooth enamel.

    PubMed

    Rodzi, Mohd; Zhumadilov, Kassym; Ohtaki, Megu; Ivannikov, Alexander; Bhattacharjee, Deborshi; Fukumura, Akifumi; Hoshi, Masaharu

    2011-08-01

    Background radiation dose is used in dosimetry for estimating occupational doses of radiation workers or determining radiation dose of an individual following accidental exposure. In the present study, the absorbed dose and the background radiation level are determined using the electron spin resonance (ESR) method on tooth samples. The effect of using different tooth surfaces and teeth exposed with single medical X-rays on the absorbed dose are also evaluated. A total of 48 molars of position 6-8 were collected from 13 district hospitals in Peninsular Malaysia. Thirty-six teeth had not been exposed to any excessive radiation, and 12 teeth had been directly exposed to a single X-ray dose during medical treatment prior to extraction. There was no significant effect of tooth surfaces and exposure with single X-rays on the measured absorbed dose of an individual. The mean measured absorbed dose of the population is 34 ± 6.2 mGy, with an average tooth enamel age of 39 years. From the slope of a regression line, the estimated annual background dose for Peninsular Malaysia is 0.6 ± 0.3 mGy y(-1). This value is slightly lower than the yearly background dose for Malaysia, and the radiation background dose is established by ESR tooth measurements on samples from India and Russia. PMID:21404066

  7. Distribution of tempo-dichlorotriazine spin label on immunoglobulin molecule. Interpretation of ESR spectra

    SciTech Connect

    Nezlin, R.

    1986-03-05

    Spin label TEMPO-dichlorotriazine (DT) has been used previously for determination of the rotational relaxation times of immunoglobulin (Ig) molecules and evaluation of their flexibility. Well defined outer wide extrema as well as sharp inner extrema are characteristic for ESR spectra of spin labeled Ig molecules. Such patterns of the spectrum can be accounted for either by the existence of the spin label in two states, one corresponding to its rapid and another to its restricted rotation or by varying environments of the spin label located in different areas of the Ig molecule. To choose between these possibilities, the distribution of /sup 14/C-TEMPO-DT on human IgG1(k) was studied. The same amount of the label per mg of protein was found in H and L chains as well as in the Fab fragment, and a smaller amount in the pFc'. The label was detected in most of the L chain tryptic peptides. Thus, the spin label is distributed nearly uniformly on IgG molecule, which is due to the regular distribution of amino acid residues reacted with the spin label. ESR spectra can be interpreted as a sum of individual spectra.

  8. TL and ESR of quartz from the astrobleme of Aorounga (Sahara of Chad)

    NASA Astrophysics Data System (ADS)

    Miallier, D.; Sanzelle, S.; Falguères, C.; Faïn, J.; Pilleyre, Th.; Vincent, P. M.

    The present work was intended to evaluate the time that elapsed since the meteorite fall that produced the giant astrobleme of Aorounga (Sahara of Chad). For this purpose the TL and ESR dating techniques using the additive dose method were applied to quartz grains extracted from an impactite and from a sandstone shocked and baked during the impact. The ESR Al centre was measured and resulted in an age of about 800 ka. The red TL and the blue TL showed unusual TL features: the additive dose response curves were marked by an initial saturated part followed by a second rise at around +0.5 kGy; the peaks showed erratic temperature shifts with dose; fading was observed for high temperature peaks. By comparison with previous work using samples baked by lava flows more than 1 Ma ago and presenting some of those features, it was assumed that the minimum age of the astrobleme was of the same order of magnitude. This is in agreement with other observations. A preliminary explanation for those ageing features is proposed. It is suspected that radiation induced traps contribute to the TL of the studied quartz grains. Most probably the 'malign-behaviour' of the quartz grains is also connected with shock effects.

  9. Pulsed ESR dipolar spectroscopy for distance measurements in immobilized spin labeled proteins in liquid solution

    PubMed Central

    Yang, Zhongyu; Liu, Yangping; Borbat, Peter; Zweier, Jay L.; Freed, Jack H.; Hubbell, Wayne L.

    2012-01-01

    Pulsed electron spin resonance (ESR) dipolar spectroscopy (PDS) in combination with site-directed spin labeling is unique in providing nanometer- range distances and distributions in biological systems. To date, most of the pulsed ESR techniques require frozen solutions at cryogenic temperatures to reduce the rapid electron spin relaxation rate and to prevent averaging of electron-electron dipolar interaction due to the rapid molecular tumbling. To enable measurements in liquid solution, we are exploring a triarylmethyl (TAM)-based spin label with a relatively long relaxation time where the protein is immobilized by attachment to a solid support. In this preliminary study, TAM radicals were attached via disulfide linkages to substituted cysteine residues at positions 65 and 80 or 65 and 76 in T4 lysozyme immobilized on Sepharose. Interspin distances determined using double quantum coherence (DQC) in solution are close to those expected from models, and the narrow distance distribution in each case indicates that the TAM-based spin label is relatively localized. PMID:22676043

  10. Optical measurement of the longitudinal ion distribution of bunched ion beams in the ESR

    NASA Astrophysics Data System (ADS)

    Wen, W. Q.; Lochmann, M.; Ma, X.; Bussmann, M.; Winters, D. F. A.; Nörtershäuser, W.; Botermann, B.; Geppert, C.; Frömmgen, N.; Hammen, M.; Hannen, V.; Jöhren, R.; Kühl, Th.; Litvinov, Yu. A.; Sánchez, R.; Stöhlker, Th.; Vollbrecht, J.; Weinheimer, C.; Dimopoulou, C.; Nolden, F.; Steck, M.

    2013-05-01

    An optical technique to study the longitudinal distribution of ions in a bunched ion beam circulating in a storage ring is presented. It is based on the arrival-time analysis of photons emitted after collisional excitation of residual gas molecules. The beam-induced fluorescence was investigated in the ultraviolet regime with a channeltron and in the visible region using a photomultiplier tube. Both were applied to investigate the longitudinal shape of bunched and electron-cooled 209Bi80+ ion beams at about 400 MeV/u in the experimental storage ring (ESR) at GSI Helmholtzzentrum für Schwerionenforschung in Darmstadt, Germany. Bunch lengths were determined with an uncertainty of about 0.5 m using the UV-sensitive channeltron and with slightly lower accuracy from the photomultiplier data due to the slower transitions in the red region of the spectrum. The Gaussian shape of the longitudinal distribution of ions inside the bunch was confirmed. With the information of the transverse beam size that can be measured simultaneously by a newly installed ionization profile monitor (IPM) at the ESR, an accurate determination of the ion density in the bunched beam will be allowed.

  11. Impact of ESR1 Gene Polymorphisms on Migraine Susceptibility: A Meta-Analysis.

    PubMed

    Li, Li; Liu, Ruozhuo; Dong, Zhao; Wang, Xiaolin; Yu, Shengyuan

    2015-09-01

    An increasing number of studies have explored genetic associations between the functionally important polymorphisms in estrogen receptor 1 (ESR1) gene and migraine susceptibility. The previously reported associations have nevertheless been inconsistent.The present work incorporating the published data derived from 8 publications was performed to assess the impact of these polymorphisms on incident migraine. Strength of the genetic risk was estimated by means of an odds ratio along with the 95% confidence interval (OR and 95% CI).From the results, we found individuals who harbored the 325-GG genotype, compared with those harboring the CC genotype or CG and CC combined genotypes, had almost 50% greater risk of migraine. The same genetic models showed notable associations in subgroups of Caucasians and migraine with aura (MA). For 594G>A, a moderately increased risk of migraine was seen under AG versus GG. The AA + AG versus GG model, however, showed a borderline association with migraine. Subgroup analyses according to ethnicity and subtype of migraine provided statistical evidence of significantly increased risk of migraine in Caucasians and of a marginal association with MA, respectively. Both 325C>G and 594G>A polymorphisms showed no major effects either in males or in females.Based on the statistical data, we conclude some of the ESR1 gene polymorphisms may have major contributions to the pathogenesis of migraine in Caucasian populations. PMID:26334887

  12. The radiation chemistry of ultem at 77 K as revealed by ESR spectroscopy

    NASA Astrophysics Data System (ADS)

    Devasahayam, Sheila; Hill, David J. T.; Pomery, Peter J.; Whittaker, Andrew K.

    2002-07-01

    Radical formation in ultem following γ-radiolysis has been reassessed, and the G( R*) values at different temperatures have been determined by ESR spectroscopy. The radical assignment and radical reactivity have been re-examined by photobleaching and thermal annealing studies. Photobleachable radical anions were found to comprise ≈40% of the total number of radicals formed on radiolysis at 77 K. Spectral subtraction methods, ESR spectral simulations, measurement of g-values and the hyperfine splitting constants were used to identify the other radical intermediates. The principal chain scission radicals are formed due to scission of the main-chain at (i) the ether linkage, (ii) the isopropylidene group and (iii) the imide ring in the main chain. The side chain methyl groups of the isopropylidine units also lose hydrogen to form methylene radicals. The five-line spectrum observed to decay in the temperature range 370-430 K, which has not been assigned previously, has been identified as being characteristic of a di-substituted benzyl radical.

  13. Evolution of atomic structure in Al75Cu25 liquid from experimental and ab initio molecular dynamics simulation studies.

    PubMed

    Xiong, L H; Yoo, H; Lou, H B; Wang, X D; Cao, Q P; Zhang, D X; Jiang, J Z; Xie, H L; Xiao, T Q; Jeon, S; Lee, G W

    2015-01-28

    X-ray diffraction and electrostatic levitation measurements, together with the ab initio molecular dynamics simulation of liquid Al(75)Cu(25) alloy have been performed from 800 to 1600 K. Experimental and ab initio molecular dynamics simulation results match well with each other. No abnormal changes were experimentally detected in the specific heat capacity over total hemispheric emissivity and density curves in the studied temperature range for a bulk liquid Al(75)Cu(25) alloy measured by the electrostatic levitation technique. The structure factors gained by the ab initio molecular dynamics simulation precisely coincide with the experimental data. The atomic structure analyzed by the Honeycutt-Andersen index and Voronoi tessellation methods shows that icosahedral-like atomic clusters prevail in the liquid Al(75)Cu(25) alloy and the atomic clusters evolve continuously. All results obtained here suggest that no liquid-liquid transition appears in the bulk liquid Al(75)Cu(25) alloy in the studied temperature range. PMID:25524926

  14. Theoretical study of stability and reaction mechanism of CuO supported on ZrO2 during chemical looping combustion

    NASA Astrophysics Data System (ADS)

    Wang, Minjun; Liu, Jing; Shen, Fenghua; Cheng, Hao; Dai, Jinxin; Long, Yan

    2016-03-01

    The addition of inert support is important for the Cu-based oxygen carrier used in chemical looping combustion (CLC). The effects of the ZrO2 support on the stability and reactivity of Cu-based oxygen carrier were investigated using the density functional theory (DFT). First, the sintering inhibition mechanism of ZrO2 that support active CuO was investigated. The optimized Cu4O4/ZrO2 structure showed a strong interaction occurred between the Cu4O4 cluster and ZrO2(1 0 1) surface. The interaction prevented the migration and agglomeration of CuO. Next, the adsorption of CO on Cu4O4/ZrO2 and the mechanism of the CuO/ZrO2 reduction by CO were studied. CO mainly chemisorbed on the Cu site and ZrO2 acted as an electron donor in the adsorption system. The energy barrier of CuO/ZrO2 reduction by CO (0.79 eV) was much lower than that of the pure CuO cluster (1.44 eV), indicating that ZrO2 had a positive effect on CuO/ZrO2 reduction by CO. After CO was oxidized in the fuel reactor, the CuO was reduced into Cu. The adsorption of O2 on Cu2/ZrO2 and the most likely pathway of Cu2/ZrO2 oxidation by O2 were investigated. The adsorption of O2 was found a strong chemisorption behavior. The energy barriers were low enough for the Cu-based oxygen carrier oxidation reaction.

  15. First-principles study of defect formation in the photovoltaic semiconductor Cu2SnS3 for comparison with Cu2ZnSnS4 and CuInSe2

    NASA Astrophysics Data System (ADS)

    Nishihara, Hironori; Maeda, Tsuyoshi; Shigemi, Akio; Wada, Takahiro

    2016-04-01

    The formation energies of neutral Cu, Sn, and S vacancies in monoclinic Cu2SnS3 were calculated by first-principles pseudopotential calculations using plane-wave basis functions in typical points in a schematic ternary phase diagram of a Cu-Sn-S system. The formation energy of a Cu atom vacancy in Cu2SnS3 under the Cu-poor condition has been calculated to be 0.23 eV, which is considerably smaller than those of Sn and S vacancies in Cu2SnS3. The results have been compared with those in Cu2SnZnS4 and CuInSe2 calculated with the same version of program code. The formation energy of a Cu atom vacancy in Cu2SnS3 under the Cu-poor condition is smaller than those for Cu2SnZnS4 (0.40 eV) and CuInSe2 (0.50 eV). The results indicate that Cu vacancies are easily formed in Cu2SnS3 under the Cu-poor condition as is the case with Cu2ZnSnS4 and CuInSe2. In this respect, Cu2SnS3 has the appropriate character of a light-absorbing material for thin-film solar cells, as is the case with Cu2ZnSnS4 and CuInSe2.

  16. Electrically-detected ESR in silicon nanostructures inserted in microcavities

    SciTech Connect

    Bagraev, Nikolay; Danilovskii, Eduard; Gets, Dmitrii; Klyachkin, Leonid; Kudryavtsev, Andrey; Kuzmin, Roman; Malyarenko, Anna; Gehlhoff, Wolfgang; Mashkov, Vladimir; Romanov, Vladimir

    2014-02-21

    We present the first findings of the new electrically-detected electron spin resonance technique (EDESR), which reveal the point defects in the ultra-narrow silicon quantum wells (Si-QW) confined by the superconductor δ- barriers. This technique allows the ESR identification without application of an external cavity, as well as a high frequency source and recorder, and with measuring the only response of the magnetoresistance, with internal GHz Josephson emission within frameworks of the normal-mode coupling (NMC) caused by the microcavities embedded in the Si-QW plane.

  17. Electrically-detected ESR in silicon nanostructures inserted in microcavities

    NASA Astrophysics Data System (ADS)

    Bagraev, Nikolay; Danilovskii, Eduard; Gehlhoff, Wolfgang; Gets, Dmitrii; Klyachkin, Leonid; Kudryavtsev, Andrey; Kuzmin, Roman; Malyarenko, Anna; Mashkov, Vladimir; Romanov, Vladimir

    2014-02-01

    We present the first findings of the new electrically-detected electron spin resonance technique (EDESR), which reveal the point defects in the ultra-narrow silicon quantum wells (Si-QW) confined by the superconductor δ- barriers. This technique allows the ESR identification without application of an external cavity, as well as a high frequency source and recorder, and with measuring the only response of the magnetoresistance, with internal GHz Josephson emission within frameworks of the normal-mode coupling (NMC) caused by the microcavities embedded in the Si-QW plane.

  18. Association of the Estrogen Receptor 1 (ESR1) Gene with Body Height in Adult Males from Two Swedish Population Cohorts

    PubMed Central

    Dahlgren, Andreas; Lundmark, Per; Axelsson, Tomas; Lind, Lars; Syvänen, Ann-Christine

    2008-01-01

    Human body height is a complex genetic trait with high heritability. We performed an association study of 17 candidate genes for height in the Uppsala Longitudinal Study of Adult Men (ULSAM) that consists of 1153 elderly men of age 70 born in the central region of Sweden. First we genotyped a panel of 137 single nucleotide polymorphism (SNPs) evenly distributed across the candidate genes in the ULSAM cohort. We identified 4 SNPs in the estrogen receptor gene (ESR1) on chromosome 6q25.1 with suggestive signals of association (p<0.05) with standing body height. This result was followed up by genotyping the same 25 SNPs in the ESR1 gene as in ULSAM in a second population cohort, the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) cohort that consist of 507 males and 509 females of age 70 from the same geographical region as ULSAM. One SNP, rs2179922 located in intron 4 of ESR1 showed and association signal (p = 0.0056) in the male samples from the PIVUS cohort. Homozygote carriers of the G-allele of the SNP rs2179922 were on average 0.90 cm taller than individuals with the two other genotypes at this SNP in the ULSAM cohort and 2.3 cm taller in the PIVUS cohort. No association was observed for the females in the PIVUS cohort. PMID:18350145

  19. Recurrent ESR1-CCDC170 rearrangements in an aggressive subset of estrogen-receptor positive breast cancers

    PubMed Central

    Veeraraghavan, Jamunarani; Tan, Ying; Cao, Xi-Xi; Kim, Jin-Ah; Wang, Xian; Chamness, Gary C.; Maiti, Sourindra N.; Cooper, Laurence J. N.; Edwards, Dean P.; Contreras, Alejandro; Hilsenbeck, Susan G.; Chang, Eric C.; Schiff, Rachel; Wang, Xiao-Song

    2014-01-01

    Characterizing the genetic alterations leading to the more aggressive forms of estrogen receptor positive (ER+) breast cancers are of critical significance in breast cancer management. Here we identify recurrent rearrangements between estrogen receptor gene ESR1 and its neighbor CCDC170, which are enriched in the more aggressive and endocrine-resistant luminal-B tumors, through large-scale analyses of breast cancer transcriptome and copy number alterations. Further screening of 200 ER+ breast cancers identifies eight ESR1-CCDC170 positive tumors. These fusions encode N-terminally truncated CCDC170 proteins (ΔCCDC170). When introduced into ER+ breast cancer cells, ΔCCDC170 leads to markedly increased cell motility and anchorage-independent growth, reduced endocrine sensitivity, and enhanced xenograft tumor formation. Mechanistic studies suggest that ΔCCDC170 engages Gab1 signalosome to potentiate growth factor signaling and enhance cell motility. Together, this study identifies neoplastic ESR1-CCDC170 fusions in a more aggressive subset of ER+ breast cancer, which suggests a new concept of ER pathobiology in breast cancer. PMID:25099679

  20. ESR response of CFQ-Gd2O3 dosimeters to a mixed neutron-gamma field: Monte Carlo simulation.

    PubMed

    Hoseininaveh, M; Ranjbar, A H

    2015-11-01

    Clear fused quartz (CFQ) may be considered a suitable material for electron and gamma dose measurements using electron spin resonance (ESR) technique. Research has been ongoing to optimize the neutron capture therapy (NCT) mechanism and its effects in cancer treatment. Neutron sources of the mixed neutron-gamma field are a challenge for this treatment method. A reliable dosimetric measurement and treatment should be able to determine various components of this mixed field. In this study, the ESR response of cylindrical and spherical shells of CFQ dosimeters, filled with Gd2O3, when exposed to a thermal neutron beam, has been investigated using Monte Carlo simulation. In order to maximize the ESR response, the dimensions of the outer and inner parts of the samples have been chosen as variables, and the amount of energy deposited in the samples has been determined. The optimum size of the samples has been determined, and the capability of discriminating gamma and neutron dose in a mixed neutron-gamma field regarding the CFQ-Gd2O3 dosimeter has also been widely studied. PMID:26342935

  1. The p-type conduction mechanism in Cu2O: a first principles study.

    PubMed

    Nolan, Michael; Elliott, Simon D

    2006-12-01

    Materials based on Cu2O are potential p-type transparent semiconducting oxides. Developing an understanding of the mechanism leading to p-type behaviour is important. An accepted origin is the formation of Cu vacancies. However, the way in which this mechanism leads to p-type properties needs to be investigated. This paper presents a first principles analysis of the origin of p-type semiconducting behaviour in Cu2O with 1.5 and 3% Cu vacancy concentrations. Plane wave density functional theory (DFT) with the Perdew-Burke Ernzerhof (PBE) exchange-correlation functional is applied. In order to investigate the applicability of DFT, we firstly show that CuO, with 50% Cu vacancies cannot be described with DFT and in order to obtain a consistent description of CuO, the DFT + U approach is applied. The resulting electronic structure is consistent with experiment, with a spin moment of 0.64 mu(B) and an indirect band gap of 1.48 eV for U = 7 eV. However, for a 3% Cu vacancy concentration in Cu2O, the DFT and DFT + U descriptions of Cu vacancies are similar, indicating that DFT is suitable for a small concentration of Cu vacancies; the formation energy of a Cu vacancy is no larger than 1.7 eV. Formation of Cu vacancies produces delocalised hole states with hole effective masses consistent with the semiconducting nature of Cu2O. These results demonstrate that the p-type semiconducting properties observed for Cu2O are explained by a small concentration of Cu vacancies. PMID:19810413

  2. Dynamical properties of the sine-Gordon quantum spin magnet Cu-PM at zero and finite temperature

    NASA Astrophysics Data System (ADS)

    Tiegel, Alexander C.; Honecker, Andreas; Pruschke, Thomas; Ponomaryov, Alexey; Zvyagin, Sergei A.; Feyerherm, Ralf; Manmana, Salvatore R.

    2016-03-01

    The material copper pyrimidine dinitrate (Cu-PM) is a quasi-one-dimensional spin system described by the spin-1/2 X X Z Heisenberg antiferromagnet with Dzyaloshinskii-Moriya interactions. Based on numerical results obtained by the density-matrix renormalization group, exact diagonalization, and accompanying electron spin resonance (ESR) experiments we revisit the spin dynamics of this compound in an applied magnetic field. Our calculations for momentum and frequency-resolved dynamical quantities give direct access to the intensity of the elementary excitations at both zero and finite temperature. This allows us to study the system beyond the low-energy description by the quantum sine-Gordon model. We find a deviation from the Lorentz invariant dispersion for the single-soliton resonance. Furthermore, our calculations only confirm the presence of the strongest boundary bound state previously derived from a boundary sine-Gordon field theory, while composite boundary-bulk excitations have too low intensities to be observable. Upon increasing the temperature, we find a temperature-induced crossover of the soliton and the emergence of new features, such as interbreather transitions. The latter observation is confirmed by our ESR experiments on Cu-PM over a wide range of the applied field.

  3. Synthesis and structural characterization of new Cu(I) complexes with the antithyroid drug 6-n-propyl-thiouracil. study of the Cu(I)-catalyzed intermolecular cycloaddition of iodonium ylides toward benzo[b]furans with pharmaceutical implementations.

    PubMed

    Paizanos, K; Charalampou, D; Kourkoumelis, N; Kalpogiannaki, D; Hadjiarapoglou, L; Spanopoulou, A; Lazarou, K; Manos, M J; Tasiopoulos, A J; Kubicki, M; Hadjikakou, S K

    2012-11-19

    The reaction of copper(I) iodide with 6-n-propylthiouracil (ptu) in the presence or absence of the triphenylphosphine (tpp) or tri(p-tolyl)phosphine (tptp) in a 1:1:2 molar ratio forms the mixed ligand Cu(I) complex with formula [CuI(ptu)2](toluene) (1), [CuI(tpp)2(ptu)] (2), and [CuI(tptp)2(ptu)] (3). The complexes have been characterized by FT-IR, (1)H NMR, UV-vis, spectroscopic techniques, and single crystal X-ray crystallography. Two sulfur atoms from two ptu ligands and one iodide form a trigonal geometry around the metal center in 1. Intramolecular interactions through hydrogen bonds lead to a bend ribbon polymeric supramolecular architecture with zigzag conformation. Two phosphorus atoms from two arylphosphines, one sulfur atom, and one iodide anion form a tetrahedron around the copper ion in case of 2 and 3. Intramolecular hydrogen bonding interactions lead to dimerization. Complexes 1-3 and the already known ones with formulas, [(tpSb)2Cu(μ2-I)2Cu(tpSb)2] (4) (tbSb = triphenylstibine), [(tpp)Cu(μ2-I)2Cu(tpp)2] (5), [(tpp)Cu(μ2-Cl)2Cu(tpp)2] (6), [CuCl(tpp)3·(CH3CN)] (7), and [AuCl(tpp)] (8), were used to study their catalytic activity on the intermolecular cycloaddition of iodonium ylides toward benzo[b]furans formation. The results show that both the metal and the ligand type affect the catalytic affinity of the complexes. The highest yield of benzo[b]furan was derived when complexes 2, 3, and 4 were used as catalysts. The mechanism of the Cu(I)-catalyzed and uncatalyzed intramolecular cycloaddition of iodonium ylide has been also thoroughly explored by means of ab initio electronic structure calculation methods, and the results are compared with the experimental ones. PMID:23110634

  4. Estrogen receptor alpha (ESR1)-signaling regulates the expression of the taxane-response biomarker PRP4K.

    PubMed

    Lahsaee, Sara; Corkery, Dale P; Anthes, Livia E; Holly, Alice; Dellaire, Graham

    2016-01-01

    The pre-mRNA splicing factor 4 kinase PRP4K (PRPF4B), is an essential kinase that is a component of the U5 snRNP and functions in spliceosome assembly. We demonstrated that PRP4K is a novel biological marker for taxane response in ovarian cancer patients and reduced levels of PRP4K correlate with intrinsic and acquired taxane resistance in both breast and ovarian cancer. Breast cancer treatments are chosen based on hormone and growth factor receptor status, with HER2 (ERBB2) positive breast cancer patients receiving anti-HER2 agents and taxanes and estrogen receptor alpha (ESR1) positive (ER+) breast cancer patients receiving anti-estrogen therapies such as tamoxifen. Here we demonstrate that PRP4K is expressed in the normal mammary duct epithelial cells of the mouse, and that estrogen induces PRP4K gene and protein expression in ER+ human MCF7 breast cancer cells. Estrogen acts through ESR1 to regulate PRP4K expression, as over-expression of ESR1 in the ER-negative MDA-MB-231 breast cancer cell line increased the expression of this kinase, and knock-down of ESR1 in ER+ T47D breast cancer cells reduced PRP4K levels. Furthermore, treatment with 4-hydroxytamoxifen (4-OHT) resulted in a dose-dependent decrease in PRP4K protein expression in MCF7 cells. Consistent with our previous studies identifying PRP4K as a taxane-response biomarker, reduced PRP4K expression in 4-OHT-treated cells correlated with reduced sensitivity to paclitaxel. Thus, PRP4K is novel estrogen regulated kinase, and its levels can be reduced by 4-OHT in ER+ breast cancer cells altering their response to taxanes. PMID:26712520

  5. Voids in fast-neutron-irradiated Cu, Ni and Cu-Ni concentrated alloys studied by TEM and positron annihilation methods

    NASA Astrophysics Data System (ADS)

    Fukushima, H.; Ochiai, K.; Shimomura, Y.

    The effect of concentrated Ni and Cu solute atoms in the Cu-Ni system on the formation of voids has been examined using Cu, Cu-8 at.% Ni, Ni-8 at.% Cu and Ni irradiated with fast-neutrons in the FFTF-MOTA. Both solute atoms introduced smaller voids in the grains of the concentrated alloys than voids in the normal grains of pure-Cu and pure-Ni. Slight increase of irradiation temperature and the higher dose of fast-neutrons induced coalescence of voids in the grains of Ni-8 at.% Cu, but it resulted in the abrupt decrease of the concentration of small voids in the grains and the formation of heterogeneously distributed larger voids near grain boundaries in Cu-8 at.% Ni. Heterogeneous distribution of larger voids was also observed in other materials. Annealing at higher temperatures induced segregation of impurity atoms at a void surface in Ni-8 at.% Cu.

  6. Theoretical study on magnetic coupling interaction for Cu(II) binuclear systems with extended bridging groups

    NASA Astrophysics Data System (ADS)

    Bi, Siwei; Liu, Chengbu; Hu, Haiquan; Zhang, Changqiao

    2001-12-01

    The magnetic coupling interaction for Cu(II) binuclear systems with bridging groups C2O4 2- , C2O2( NH) 2 2- ( cis), C2O2( NH) 2 2- ( trans) and C2S2( NH) 2 2- ( trans) was studied by the broken symmetry (BS) approach within the framework of the density functional theory (DFT). The influence of different coordination atoms and geometry on magnetic coupling interaction was theoretically analyzed. Both of the calculated and experimental results were compared. The variation trends of coupling interaction calculated are in agreement with experimental ones.

  7. A detailed study of the magnetic phase transition in CuCrO2.

    PubMed

    Ehlers, G; Podlesnyak, A A; Frontzek, M; Freitas, R S; Ghivelder, L; Gardner, J S; Shiryaev, S V; Barilo, S

    2013-12-11

    The phase transition in CuCrO2 to an ordered magnetic state is studied with bulk measurements and elastic and inelastic neutron scattering techniques. The reported onset of spontaneous electric polarization at T = 23.5 K coincides with the appearance, on cooling, of elastic magnetic scattering. At higher temperatures long range magnetic correlations gradually develop but they are dynamic. The ground state is characterized by three-dimensional long range magnetic ordering but along the c direction the correlation length remains limited to ∼200 Å. PMID:24214902

  8. DFT study of isocyanate chemisorption on Cu(100): Correlation between substrate-adsorbate charge transfer and intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Belelli, Patricia G.; Garda, Graciela R.; Ferullo, Ricardo M.

    2011-07-01

    The adsorption of isocyanate (- NCO) species on Cu(100) was studied using the density functional theory (DFT) and the periodic slab model. The calculations indicate that at low and intermediate coverages NCO adsorbs preferentially on bridge and hollow sites. Work function and dipole moment changes show a significant negative charge transfer from Cu to NCO. The resulting charged NCO species interact repulsively among themselves being these dipole-dipole interactions particularly intensive when they are adsorbed in adjacent sites. Consequently, isocyanates tend to be separated from each other generating the vacant sites required for the dissociation to N and CO. This condition for NCO dissociation has been suggested in the past from experimental observations. A comparison was also performed with the NCO adsorption on Pd(100). In particular, the calculated minimal energy barrier for NCO dissociation was found to be higher on Cu(100) than on Pd(100) in accord with the well known higher NCO stability on Cu(100).

  9. XPS study of the chemical stability of DyBa2Cu3O6+δ superconductor

    NASA Astrophysics Data System (ADS)

    Fetisov, A. V.; Kozhina, G. А.; Estemirova, S. Kh.; Fetisov, V. B.; Gulyaeva, R. I.

    2015-01-01

    The chemical stability of the powder DyBa2Cu3O6+δ has been studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and thermal analysis at ambient conditions. The powder was subjected to mechanical processing in a ball mill-activator to accelerate chemical degradation. The kinetic regularities of hydrolytic decomposition of DyBa2Cu3O6+δ under the influence of air moisture have been determined. The resistive properties of DyBa2Cu3O6+δ to water have been found to be better, but not much different from analogous properties of YBa2Cu3O6+δ which is unstable in a wet environment. Chemical degradation of the material is triggered by crucial concentrating of water particles near the free surface of the solid reactant (due to their low diffusibility in the bulk) leading to rapid chemical decomposition of the respective regions.

  10. Effect of electron- and neutron-irradiation on Fe-Cu model alloys studied by positron annihilation spectroscopy

    NASA Astrophysics Data System (ADS)

    Nagai, Y.; Takadate, K.; Tang, Z.; Ohkubo, H.; Sunaga, H.; Takizawa, H.; Hasegawa, M.

    2011-01-01

    Electron- and neutron-irradiation effects on dilute Fe-Cu model alloys of nuclear reactor pressure vessel steels are studied by positron annihilation spectroscopy. We have found that, not only by high-dose neutron-irradiation but also by low-dose electron-irradiation, the aggregation of Cu atoms and vacancies takes place and the ultrafine Cu precipitates are formed after post-irradiation annealing at 400°C. In spite of large difference in the irradiation doses between the electron- and the neutron-irradiated samples, no significant difference is observed in the isochronal annealing behaviour above 400°C of positron annihilation and micro-hardness, indicating that small amount of extra vacancies enhance the aggregation of Cu atoms in Fe during the annealing-out process of the vacancies.

  11. Optical spectroscopy study of pulsed excimer laser generated plasma from CuO

    SciTech Connect

    Adhi, K.P.; Kale, S.; Padhye, Y.; Limaye, A.V.; Ogale, S.B.

    1995-12-15

    Optical emissions from pulsed excimer laser induced plasma emanating from CuO target are studied by an Optical Multichannel Analyzer system in the context of its implications for thin film growth by Pulsed Laser Deposition. The plasma is generated in four different ambients viz. hydrogen, helium, oxygen (pressure of 100 mTorr in each case) and vacuum (2 {times} 10{sup {minus}5} Torr) at different energy densities from 1 to 3.5 J/cm{sup 2}. The plasma constituents and their evolution in the growth space (i.e. at a distance of 1.5 cm from the target) has been studied. Various transitions corresponding to Cu(I), H(I), Cu(II) and O(II) are observed. The observation of strong transitions due to O(II) in the plasma formed in vacuum, hydrogen and helium suggests significant degree of ionization of atoms via molecular splitting and inverse Bremsstrahlung process during early plasma formation. The persistence of ionicity in the plasma can be attributed to long recombination lifetimes for the specific conditions used. In the case of ablation in oxygen ambient a very significant and remarkably selective enhancement of the copper vapor lasing transition at 510.5 nm is observed which brings out the role of oxygen molecules in sustaining the radiation trapping condition. The changes in the concentrations of neutrals and ions are a function of the laser energy density are also examined. It is argued that impingement of ions/atoms in an excited state on the growing surface can potentially lead to localized energy deposition via non-radiative deexcitation resulting into enhancement of film quality and density.

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

    SciTech Connect

    Zhang, Renqin; McEwen, Jean-Sabin; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2014-11-07

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

  13. Stabilization of Pb and Cu in contaminated soils using (nano)oxides - a preliminary study

    NASA Astrophysics Data System (ADS)

    Komárek, Michael; Michálková, Zuzana; Vaněk, Aleš

    2013-04-01

    Chemical stabilization techniques (the application of various stabilizing amendments, which by chemical means reduces contaminant mobility, bioavailability and bioaccessibility) have shown to be possible less destructive alternatives to conventional remediation options. Most stabilization techniques aim at rendering less available the metal(loid) fractions that can pose significant environmental and/or toxicological risks and protecting the functionality of the soil environment. Nano-particulate oxides (particle size of 1-100 nm) are important scavengers of contaminants in soils and due to their reactive and relatively large specific surface area, engineered oxide nanoparticles are promising materials for the remediation of soils contaminated with inorganic pollutants. However, studies assessing the efficiency of these amendments in contaminated soils are still rather scarce. Therefore, the aim of this work is to evaluate the stabilization efficiency of four (nano)oxides (maghemite, magnetite, gibbsite and amorphous Mn oxide (AMO)) in two soils contaminated with Cu (400 mg/kg; pH 3.6) and Pb (1500 mg/kg; pH 5.5), respectively, using chemical extraction methods (CaCl2, EDTA and the BCR sequential extraction) and direct sampling of soil solution using rhizons. The results suggest that the application of the oxides did not influence the pH of the soils, with the only exception of the AMO, which increased the pH and resulted into the formation of MnCO3 on the oxide surface (data from SEM and XRD). Additionally, the high reactivity of the oxides led to increased DOC concentrations originating from the dissolved soil organic matter, especially in the case of the AMO. The AMO was also the most efficient stabilizing amendment for Cu (most significant decrease in Cu in soil solution, in the exchangeable fraction and CaCl2/EDTA extracts), promoted by the pH increase. Despite their lower particle size, maghemite, magnetite and gibbsite were less efficient; although partial

  14. Surface chemistry of a Cu(I) beta-diketonate precursor and the atomic layer deposition of Cu{sub 2}O on SiO{sub 2} studied by x-ray photoelectron spectroscopy

    SciTech Connect

    Dhakal, Dileep; Waechtler, Thomas; Schulz, Stefan E.; Gessner, Thomas; Lang, Heinrich; Mothes, Robert; Tuchscherer, André

    2014-07-01

    The surface chemistry of the bis(tri-n-butylphosphane) copper(I) acetylacetonate, [({sup n}Bu{sub 3}P){sub 2}Cu(acac)] and the thermal atomic layer deposition (ALD) of Cu{sub 2}O using this Cu precursor as reactant and wet oxygen as coreactant on SiO{sub 2} substrates are studied by in-situ x-ray photoelectron spectroscopy (XPS). The Cu precursor was evaporated and exposed to the substrates kept at temperatures between 22 °C and 300 °C. The measured phosphorus and carbon concentration on the substrates indicated that most of the [{sup n}Bu{sub 3}P] ligands were released either in the gas phase or during adsorption. No disproportionation was observed for the Cu precursor in the temperature range between 22 °C and 145 °C. However, disproportionation of the Cu precursor was observed at 200 °C, since C/Cu concentration ratio decreased and substantial amounts of metallic Cu were present on the substrate. The amount of metallic Cu increased, when the substrate was kept at 300 °C, indicating stronger disproportionation of the Cu precursor. Hence, the upper limit for the ALD of Cu{sub 2}O from this precursor lies in the temperature range between 145 °C and 200 °C, as the precursor must not alter its chemical and physical state after chemisorption on the substrate. Five hundred ALD cycles with the probed Cu precursor and wet O{sub 2} as coreactant were carried out on SiO{sub 2} at 145 °C. After ALD, in-situ XPS analysis confirmed the presence of Cu{sub 2}O on the substrate. Ex-situ spectroscopic ellipsometry indicated an average film thickness of 2.5 nm of Cu{sub 2}O deposited with a growth per cycle of 0.05 Å/cycle. Scanning electron microscopy and atomic force microscopy (AFM) investigations depicted a homogeneous, fine, and granular morphology of the Cu{sub 2}O ALD film on SiO{sub 2}. AFM investigations suggest that the deposited Cu{sub 2}O film is continuous on the SiO{sub 2} substrate.

  15. A theoretical study of CO and NO interaction with Cu sites in ZSM-5: Electronic structure and vibrational spectra

    SciTech Connect

    Ramprasad, R.; Hass, K.C.; Schneider, W.F.

    1996-10-01

    The interaction of CO and NO with various Cu sites in zeolites were studied theoretically within the framework of density functional theory. Our models of the active sites are simple charged clusters, with Cu ions coordinated to a certain number of water ligands and in some cases to a hydroxyl ligand in addition to water ligands. We have studied the electronic and geometric structure of monocarbonyl, mono- and dinitrosyl complexes. We find that in all mono- and dinitrosyl complexes that we considered, the Cu preferred to be in its 1+ oxidation state, irrespective of the overall cluster charge or the degree of coordination resulting in three different binding modes. We have also performed vibrational frequency calculations for the optimal monocarbonyl, mono- and dinitrosyl geometries. Of all the complexes that we considered, our results for low coordinated Cu(I) (coordinated to about 2 water ligands) and hydroxyl ligand coordinated Cu(II) are consistent with experimentally observed CO and NO stretch frequencies in Cu-ZSM-5.

  16. Structural and optical properties of Cu doped SnO2 nanoparticles: An experimental and density functional study

    NASA Astrophysics Data System (ADS)

    Chetri, Pawan; Saikia, Bhamyarswa; Choudhury, Amarjyoti

    2013-06-01

    The paper investigates, both theoretically and experimentally, the structural and optical changes in SnO2 system brought about by introduction of Cu in a SnO2 system. On the experimental front, a cost effective sol-gel technique is used to prepare hexagonal shaped Cu doped SnO2 nanoparticles. The prepared pristine SnO2 nanoparticle is found to be of random shape by transmission electron microscope (TEM) studies. A structural and morphological study is carried out using X-ray diffraction and TEM techniques. The different phonon interaction in the system is observed by Raman spectroscopy while electron paramagnetic resonance and UV-Visible spectroscopy confirms the presence of Cu in 2+ state. First principle calculations have been performed using "density functional theory"-based MedeA Vienna Ab Initio Simulation package on a SnO2 system where Cu is introduced. The introduction of Cu in the SnO2 system brings distortion which is corroborated by the variation in the corresponding bond lengths. The Density of State calculation of Sn16O32 and CuSn15O32 is also performed. Finally, a correlation is established between the experiment and the theory.

  17. ESR/alanine dosimetry applied to radiation processing

    NASA Astrophysics Data System (ADS)

    Mosse, D. C.

    The radiation processing of food products is specified in terms of absorbed dose, and processing quality is assessed on the basis of absorbed dose measurements. The validity of process quality control is highly dependent on the quality of the measurements and associated instrumentation; in this respect, dosimetry calibration by an Organization with official status provides an essential guarantee of validity to the quality control steps taken. The Laboratoire de Métrologie des Rayonnements Ionisants (L.M.R.I.) is the primary standards and evaluation laboratory approved by the Bureau National de Métrologie (B.N.M.), which is the French National Bureau of Standards. The LMRI implements correlation procedures in response to the various requirements which arise in connection with high doses and doserates. Such procedures are mainly based on ESR/alanine spectrometry, a dosimetry technique ideally suited to that purpose. Dosemeter geometry and design are tailored to operating conditions. "Photon" dosemeters consist of a detector material in powder or compacted form, and a wall with thickness and chemical composition consistent with the application. "Electron" dosemeters have a detector core of compacted alanine with thickness down to a few tenths of a millimeter. The ESR/alanine dosimetry technique, developed at LMRI is a flexible, reliable and accurate tool which effectively meets the various requirements arising in the field of reference dosimetry, where high doses and doserates are involved.

  18. Tetra- and hexadentate Schiff base ligands and their Ni(II), Cu(II) and Zn(II) complexes. Synthesis, spectral, magnetic and thermal studies.

    PubMed

    Ismail, Tarek M A; Saleh, Akila A; El Ghamry, Mosad A

    2012-02-01

    Tetradentate N(2)O(2), N(4) Schiff bases, 1,2-bis(4-oxopent-2-ylideneamino) benzene (BOAB), 1-(4-oxopent-2-ylideneamino-2-[(2-hydroxyphenyl)ethylideneamino] benzene (OAHAB), 7,16-bis(4-chlorobenzylidene)-6,8,15,17-tetra-methyl-7,16-dihydro -5,9,14,18-tetraza-dibenzo[a,h] cyclo tetradecene (BCBDCT), 7,16-bis(2-hydroxy-benzylidene)-6,8,15,17-tetramethyl-7,16-dihydro-5,9,14,18-tetraza-dibenzo [a,h] cyclo tetradecene (BHBDCT) and hexadentate N(4)O(2) Schiff bases, 2,4-bis {2-[1-(2-hydroxyphenyl) ethylideneamino] phenylimino}-3-(2-hydroxybenzylidene) pentane (BHAPHP), 2,4-bis {2-[1-(2-hydroxyphenyl) ethylideneamino] phenylimino}-3-(4-chlorobenzylidene) pentane (BHAPCP) were prepared and characterized by elemental analysis, IR, UV-Vis, (1)H NMR and mass spectra. The solid complexes of the prepared Schiff base ligands with Ni(II), Cu(II) and Zn(II) ions were isolated and characterized by elemental and thermal analyses, IR, electronic and ESR spectra as well as conductance and magnetic susceptibility measurements. The results showed that most complexes have octahedral geometry but few can attain the tetrahedral arrangement. The TG analyses suggest high stability for most complexes followed by thermal decomposition in different steps. The kinetic and thermodynamic parameters for decomposition steps in Cu(II) complexes thermograms have been calculated. PMID:22070996

  19. Tetra- and hexadentate Schiff base ligands and their Ni(II), Cu(II) and Zn(II) complexes. Synthesis, spectral, magnetic and thermal studies

    NASA Astrophysics Data System (ADS)

    Ismail, Tarek M. A.; Saleh, Akila A.; Ghamry, Mosad A. El

    2012-02-01

    Tetradentate N 2O 2, N 4 Schiff bases, 1,2-bis(4-oxopent-2-ylideneamino) benzene (BOAB), 1-(4-oxopent-2-ylideneamino-2-[(2-hydroxyphenyl)ethylideneamino] benzene (OAHAB), 7,16-bis(4-chlorobenzylidene)-6,8,15,17-tetra-methyl-7,16-dihydro -5,9,14,18-tetraza-dibenzo[a,h] cyclo tetradecene (BCBDCT), 7,16-bis(2-hydroxy-benzylidene)-6,8,15,17-tetramethyl-7,16-dihydro-5,9,14,18-tetraza-dibenzo [a,h] cyclo tetradecene (BHBDCT) and hexadentate N 4O 2 Schiff bases, 2,4-bis {2-[1-(2-hydroxyphenyl) ethylideneamino] phenylimino}-3-(2-hydroxybenzylidene) pentane (BHAPHP), 2,4-bis {2-[1-(2-hydroxyphenyl) ethylideneamino] phenylimino}-3-(4-chlorobenzylidene) pentane (BHAPCP) were prepared and characterized by elemental analysis, IR, UV-Vis, 1H NMR and mass spectra. The solid complexes of the prepared Schiff base ligands with Ni(II), Cu(II) and Zn(II) ions were isolated and characterized by elemental and thermal analyses, IR, electronic and ESR spectra as well as conductance and magnetic susceptibility measurements. The results showed that most complexes have octahedral geometry but few can attain the tetrahedral arrangement. The TG analyses suggest high stability for most complexes followed by thermal decomposition in different steps. The kinetic and thermodynamic parameters for decomposition steps in Cu(II) complexes thermograms have been calculated.

  20. Investigation of the momentum compaction factor of the ESR thorough Schottky mass measurements

    NASA Astrophysics Data System (ADS)

    Yan, X. L.; Bosch, F.; Litvinov, Yu A.; Nolden, F.; Steck, M.; Tu, X. L.; Xu, H. S.; Zhou, X. H.; Zhang, Y. H.

    2015-11-01

    Schottky mass spectrometry was applied to stored and cooled neutron-deficient 152Sm projectile fragments at the experimental storage ring (ESR) facility at GSI Darmstadt, Germany. 311 different nuclides were identified by means of their revolution frequency spectra. The measured frequencies were used to investigate the shape of the momentum-compaction-factor of the ESR.