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Sample records for cu esr studies

  1. IR and ESR study of Cu(II)-nitrazepam complexes

    NASA Astrophysics Data System (ADS)

    Forizs, E.; David, L.; Cozar, O.; Crăciun, C.; Venter, M.; Kilyen, M.

    1997-06-01

    The CuL 2X 2 (L = 7-nitro-1,3-dihydro-5-phenyl-2 H-1,4-benzodiazepin-2-one, known as nitrazepam, X = Cl, Br) complexes were prepared and investigated by IR, ESR and magnetic susceptibility measurements. The IR spectra suggest that the Cu(II) ion is coordinated by two nitrogen and two halogen atoms. The powder ESR spectrum at room temperature of CuL 2Br 2 is quasiisotropic, while that of CuL 2Cl 2 is characteristic of an axial monomeric species with small rhombic distortions. The isotropic ESR spectra of these compounds in DMF and Py solutions suggest the presence of pseudo-tetrahedral monomeric species. Two different monomeric species were evidenced in Cu(II)-nitrazepam solutions adsorbed onto NaY zeolite.

  2. ESR, spectroscopic, and quantum-chemical studies on the electronic structures of complexes formed by Cu(I) with radicals

    SciTech Connect

    Gritsan, N.P.; Usov, O.M.; Shokhirev, N.V.; Khmelinskii, I.V.; Plyusnin, V.F.; Bazhin, N.M.

    1986-07-01

    The optical and ESR spectra have been examined for complexes of Cu(I) with various radicals, which contain various numbers of Cl/sup -/ ions in the central-atom coordination sphere. The spin-Hamiltonian parameters have been determined for all these radical complexes, and the observed ESR spectra have been compared with those calculated with allowance for second-order effects. The observed values for the isotropic and anisotropic components of the HFI constant from the central ion have been used to estimate the contributions from the 4s and 3d/sup 2//sub z/ orbitals of the copper ion to the unpaired-electron MO. Quantum-chemical calculations have been performed by the INDO method on the electronic structures and geometries of complexes formed by CH/sub 2/OH with Cu(I) for various Cl/sup -/ contents in the coordination sphere. The radical is coordinated by the ..pi.. orbital on the carbon atom, and the stabilities of the radical complexes decrease as the number of Cl/sup -/ ions in the coordination sphere increases. A geometry close to planar for the CuCl/sub 4//sup 3 -/ fragment in a complex containing four Cl/sup -/ ions.

  3. Microwave absorption studies on high-T sub c superconductors and related materials 7--ESR of DPPH coated on a thin BiSrCaCuO film fabricated on MgO(100) substrate

    SciTech Connect

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

    1992-05-10

    In this paper, ESR of DPPH coated on a Bi-Sr-Ca-Cu-O (BSCCO) film (350 {Angstrom} thick) fabricated on MgO(100) substrate by MOCVD is studied. Temperature dependence of the ESR peak-to-peak linewidth, {Delta}H{sub pp}, and the effect of applied magnetic field on {Delta}H{sub pp} are below about 100 K. The results are 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 reveals that {Delta}H{sub pp} 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. Microwave absorption studies of high T sub c superconductors and related materials 8; ESR of DPPH coated on BiSrCaCuO films fabricated on MgO (100) substrates

    SciTech Connect

    Sugawara, K.; Tanaka, S. )

    1992-06-20

    This paper reports that ESR of DPPH coated on Bi-Sr-Ca-Cu-O films fabricated on MgO (100) substrates by MOCVD have been studied for samples with different thicknesses, 1000 {Angstrom} and 100 {Angstrom}. Temperature dependence of the ESR peak-to-peak linewidth, {Delta}H{sub pp}, revealed that {Delta}H{sub pp} increases with film thickness. The Excess ESR linewidth, {delta}({Delta}H{sub pp}) was also analyzed in terms of (1 {minus} t{sup alpha}, with t = T/T{sub c}, giving for example {alpha} = 4 ={minus}1 for the 1000 {Angstrom} thick sample. The ESR lineshapes were distorted by rotating the samples in applied magnetic fields. Severe distortion was found for the 1000 {Angstrom} sample below about 30 K, but the distortion almost disappears at temperatures above 30 K. The applied magnetic field effects were also examined in both field-cooled and zero-field-cooled cases.

  5. Photopolymerization study of photoresists by ESR spectroscopy and ESR imaging

    NASA Astrophysics Data System (ADS)

    Dahm, J.; Macho, V.; Maresch, G. G.; Spiess, H. W.

    Generation of radicals by UV irradiation of photoresistive materials is investigated by electron spin resonance (ESR) spectroscopy and ESR imaging. It is shown that at room temperature the polymerization process proceeds on a time scale of minutes. The ESR intensity as a function of the illumination time reaches a maximum. Further irradiation decreases the number of radicals due to recombination processes. The ESR spectrum indicates the presence of three different types of radicals which are stable at temperatures below 250 K. The ESR intensity profile from bulk photoresists measured by ESR imaging shows that the UV light is absorbed at the surface. The penetration depth for light of 300 nm wavelength amounts to 75 μm. The broad and structured ESR spectrum requires the application of deconvolution techniques in order to obtain sufficient spatial resolution. The paper discusses the limitations of standard deconvolution and the advantage of linear prediction techniques.

  6. 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.

  7. Microwave absorption studies on high-T sub c superconductors and related materials IV ESR as a probe of flux pinning in Y-Ba-Cu-O superconductors prepared by the MPMG method

    SciTech Connect

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

    1991-06-01

    This paper reports that the electron spin resonances of both DPPH surface coatings and Y{sub 2}Ba{sub 1}Cu{sub 1}O{sub 5} (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 Y{sub 2}Ba{sub 1}Cu{sub 1}O{sub 5} below 20 K, possibly due to a lower magnetic ordering temperature, mechanical stress, and/or different composition of the inclusions as compared to isolated Y{sub 2}Ba{sub 1}Cu{sub 1}O{sub 5}. 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.

  8. 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.

  9. Mobility Studies on Nitroxyl Radicals using ESR 300 MHz Spectrometer

    NASA Astrophysics Data System (ADS)

    Dhas, M. Kumara; Franklin Benial, A. Milton; Jawahar, A.

    2011-07-01

    The mobility studies on 14N labeled TEMPOL, carboxy PROXYL, carbamoyl PROXYL in pure water, pure water and glycerol at ratio (15:85) was carried out using 300 MHz ESR spectrometer. The ESR parameters such as linewidth, signal intensity ratio and correlation time were determined. The isotropic g-factor and hyperfine coupling constant were also estimated. This ESR study reveals that the dipolar and spin exchange interactions are less in the 14N labeled TEMPOL radical. This phenomenon can be explained in terms of the structural, physical and chemical properties of the TEMPOL molecule. The mobility of TEMPOL radical is not much affected by the high viscous medium. Hence the TEMPOL radical can be used as a good spin probe in high viscous medium.

  10. E.s.r., magnetic, optical and biological (SOD and antimicrobial) studies of imidazolate bridged Cu II-Zn II and Cu II-Ni II complexes with tris(2-amino ethyl)amine as capping ligand: a plausible model for superoxide dismutase

    NASA Astrophysics Data System (ADS)

    Singh, Nripendra; Shukla, K. K.; Patel, R. N.; Chauhan, U. K.; Shrivastava, R.

    2003-11-01

    X-band e.s.r. and optical absorption spectra of the imidazolate bridged heterobimetallic complexes [(tren)Cu-E-Im-Zn-(tren)](ClO 4) 3 and [(tren)Cu-E-Im-Ni-(tren)](ClO 4) 3, where trentris(2-aminoethyl)amine, E-Im=2-ethylimidazolate ion and the related mononuclear complexes [Cu(tren)](ClO 4) 2 and [(tren)Cu-E-ImH)](ClO 4) 2 have been described. Biological activities (superoxide dismutase and antimicrobial) have also been measured and compared with reported complexes.

  11. Usability of tartaric acid in dose measurements: an ESR study

    NASA Astrophysics Data System (ADS)

    Korkmaz, Güney; Polat, Mustafa; Korkmaz, Mustafa

    2010-03-01

    Unirradiated tartaric acid samples do not exhibit any ESR signal. However, the ESR spectra of irradiated samples contain many resonance signals. The dose-responce curves of the resonance signals, denoted as I 1, I 2, I 3 and I 4 in the present study, were found to increase linearly with the applied radiation dose in the range of 0.04-25 kGy. Adjusting the microvawe power and modulation amplitudes of 1.0 mW and 1.0 mT, respectively, was found to increase the sensitivity of tartaric acid. From the dose-response curves and room temperature decay data, it was concluded that the I 3 resonance signal of tartaric acid can be used for dose measurements at intermediate (0.04-0.4 kGy) and high dose (0.5-25 kGy) levels.

  12. ESR Spectroscopy Provides Direct Evidence of Cu^2+ Coordination by Three Histidine Residues in Aβ1-16

    NASA Astrophysics Data System (ADS)

    Shin, Byong-Kyu; Saxena, Sunil

    2009-03-01

    We provide direct evidence that all three histidine residues in amyloid-β1-16 (Aβ1-16) coordinate to Cu^2+. In our approach, we generate three Aβ1-16 analogues, in each of which a selected histidine residue is isotopically enriched with ^15N. Pulsed electron spin resonance (ESR) experiments such as electron spin echo envelope modulation (ESEEM) and hyperfine sublevel correlation (HYSCORE) clearly show that each of the three histidine imidazole rings at position 6, 13, and 14 in Aβ1-16 binds to Cu^2+ as each of the three Cu^2+--^15N-labeled Aβ1-16 complexes displays ESEEM and HYSCORE spectra which are distinctively different from those of the Cu^2+--nonlabeled Aβ1-16 complex. The method employed here does not require either chemical side-chain modification or amino acid residue replacement, each of which is traditionally used to determine whether an amino acid residue in a protein binds to a metal ion. We also find that the histidine coordination in Aβ1-16 is independent of the Cu^2+-to-peptide ratio, which is in contrast to the case of Aβ1-40. The ESR results suggest tight binding between the histidine residues and the Cu^2+ ion, which is likely the reason of the high binding affinity of Aβ peptide to Cu^2+.

  13. 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).

  14. 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.

  15. ESR/spin probe study of ice cream.

    PubMed

    Gillies, Duncan G; Greenley, Katherine R; Sutcliffe, Leslie H

    2006-07-12

    Spin probes based on the 1,1,3,3-tetramethylisoindolin-2-yl structure have been used, in conjunction with electron spin resonance spectroscopy (ESR), to study the physical changes occurring in ice cream during freezing and melting. The ESR measurements allowed the rotational correlation times, tau(B), of the spin probes to be determined. Two probes were used together in a given sample of ice cream, namely, 1,1,3,3-tetramethylisoindolin-2-yl (TMIO), which samples the fat phase, and the sodium salt of 1,1,3,3-tetramethylisoindolin-2-yloxyl-5-sulfonate (NaTMIOS), which samples the aqueous phase. Data from the TMIO probe showed that when ice cream is cooled, the fat phase is a mixture of solid and liquid fat until a temperature of approximately -60 degrees C is reached. The water-soluble probe NaTMIOS showed that the aqueous phase changes completely from liquid to solid within 1 degrees C of -18 degrees C. On cooling further to -24.7 degrees C and then allowing it to warm to +25.0 degrees C, the rotational correlation times of the NaTMIOS were slow to recover to their previous values. For the lipid phase, tau(B)(298) was found to be 65.7 +/- 2.0 ps and the corresponding activation enthalpy, DeltaH, was 32.5 +/- 0.9 kJ mol(-)(1): These values are typical of those expected to be found in the type of fat used to make ice cream. The water phase gave corresponding values of 32.2 +/- 0.5 ps and 24.5 +/- 0.4 kJ mol(-)(1) values, which are those expected for a sucrose concentration of 24%.

  16. Synthesis, electronic and ESR spectral studies on copper(II) nitrate complexes with some acylhydrazines and hydrazones.

    PubMed

    Singh, Vinod P

    2008-11-01

    This paper describes the preparation of [Cu(bh)2(H2O)2](NO3)2], [Cu(ibh)2(NO3)2], [Cu(ibh)2(H2O)2](NO3)2 and [Cu(iinh)2(NO3)2] (bh = benzoyl hydrazine (C6H5CONHNH2); ibh = isonicotinoyl hydrazine (NC5H4CONHNH2); ibh = isopropanone benzoyl hydrazone (C6H5CONHN=C(CH3)2; iinh = isopropanone isonicotinoyl hydrazone (NC5H4CONHN=C(CH3)2). These copper(II) complexes are characterized by elemental analyses, molar conductances, dehydration studies, ESR, IR and electronic spectral studies. The electronic and ESR spectra indicate that each complex exhibits a six-coordinate tetragonally distorted octahedral geometry in the solid state and in DMSO solution. The ESR spectra of most of the complexes are typically isotropic type at room temperature (300 K) in solid state as well as in DMSO solution. However, all the complexes exhibit invariably axial signals at 77 K in DMSO solution. The trend g(||) > g(perpendicular) > g(e,) observed in all the complexes suggests the presence of an unpaired electron in the d x2-y2 orbital of the Cu(II). The bh and inh ligands bond to Cu(II) through the >C=O and -NH2 groups whereas, ibh and iinh bond through >C=O and >C=N- groups. The IR spectra of bh and ibh complexes also show H-O-H stretching and bending modes of coordinated water.

  17. ESR study of reduced monosubstituted ruthenium(II) diimine complexes

    SciTech Connect

    Samuels, A.C.; DeArmond, M.K.

    1995-10-25

    Electron spin resonance spectroscopy (ESR) was used in the characterization of [Ru(bpy)(CN){sub 4}]{sup 2{minus}}, [Ru(bpm)(CN){sub 4}]{sup 2{minus}}, and [Ru(bpz)(CN){sub 4}]{sup 2{minus}}. Hyperfine structure and coupling constants for the ESR spectra were reported. Further characterization of these complexes was accomplished using absorption and emission spectroscopy and cyclic voltammetry.

  18. 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.

  19. 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.

  20. 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

  1. Synthesis, spectroscopic (electronic, IR, NMR and ESR) and theoretical studies of transition metal complexes with some unsymmetrical Schiff bases

    NASA Astrophysics Data System (ADS)

    Singh, Vinod P.; Singh, Shweta; Singh, Divya P.; Tiwari, K.; Mishra, Monika

    2014-01-01

    Two unsymmetrical Schiff bases, glyoxal salicylaldehyde oxalic acid dihydrazone (gsodh) and glyoxal salicylaldehyde malonic acid dihydrazone (gsmdh) and their Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. The structures of metal complexes are elucidated on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, electronic, ESR, IR and NMR (1H and 13C) spectral studies. Both ligands show monobasic tetra-dentate behaviour, bonding through CO, two CN and a phenolate group. The electronic spectral studies in solid state indicate a square planar geometry for Ni(II) and Cu(II) complexes and a tetrahedral geometry for Co(II) complexes. However, Co(II) and Cu(II) complexes adopt octahedral geometry in DMSO solution. The ESR spectra of Cu(II) complexes in DMSO solution at 77 K predict an elongated tetragonal distorted octahedral geometry around metal ion and presence of unpaired electron in d orbital. Further, the structures of ligands and their Ni(II) complexes have been satisfactorily modelled by calculations based on density functional theory (DFT). The electronic spectra of Ni(II) complexes are also analyzed in depth with the help of time dependent-DFT (TD-DFT). The theoretical analyses of electronic structure and molecular orbitals have demonstrated that the high-energy absorption bands are M → L charge transfer and low energy transitions are d-d transitions.

  2. IN SITU optical and ESR studies of polyazulene

    NASA Astrophysics Data System (ADS)

    Hayashi, S.; Nakajima, S.; Kaneto, K.; Yoshino, K.

    1986-11-01

    The neutral polyazulene shows an extraordinary large ESR spin density ≈ 10 20 spins/g and two optical absorption peaks corresponding to the interband transitions. As the doping proceeds, the spin density as a function of applied potential charges anomalously and new optical absorption peaks characteristic to each doping stage appear successively. These results are explained tentatively by taking a unique band structure of polyazulene into account.

  3. ESR Study on Irradiated Ascorbic Acid Single Crystal

    NASA Astrophysics Data System (ADS)

    Tuner, H.; Korkmaz, M.

    2007-04-01

    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.

  4. 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.

  5. Synthesis, ESR, UV-Visible and reactivity studies of new bis(N-dimethoxyaniline-3,5-(t)Bu2-salicylaldiminato)copper(II) complexes.

    PubMed

    Kasumov, Veli T; Köksal, Fevzi

    2012-12-01

    Several new copper(II) complexes (4-6) with N-dimethoxyphenyl-3,5-(t)Bu(2)-salicylaldimine ligands abbreviated as N-R-3,5-DTBS, where R=2,4-dimethoxyphenyl (1), 2,5-dimethoxyphenyl (2) and 3,5-dimethoxyphenyl (3) have been prepared and their spectroscopic (IR, (1)H NMR, UV/Vis, ESR), magnetic and redox reactivity are described. The ESR spectra of frozen-solution 4-6 and solid state 4 and 5 are indicative of axially symmetric g-tensor (g([parallel])>g([perpendicular])>2.03). The powder ESR spectrum of 6 is unusual for CuN(2)O(2) type systems and exhibits "reversed" type (g([parallel])g(2) (2.128)>g(1) (2.019) pattern indicative of a d(z)(2) ground state. Chemical oxidation of 4 and 6, as supported by ESR and UV/Vis techniques, generates new Cu(II) species and Cu(II)-phenoxyl radicals. The CV studies have shown that the complexes possess ligand-centered and copper(II)-centered quasi-reversible and irreversible responses.

  6. Luminescence (M=Mn2+, Cu2+) and Esr (M=Gd3+, Mn2+, Cu2+) of Na2ZnP2O7: M

    NASA Astrophysics Data System (ADS)

    Kumar, B. Vijaya; Vithal, M.

    2012-06-01

    We report the synthesis of sodium zinc diphosphate (Na2ZnP2O7) using a domestic microwave oven (2.45 GHz) and metal ion doped sodium zinc diphosphate (Na1.88Gd0.04ZnP2O7/Na1.92M0.04ZnP2O7 (M=Mn and Cu)) by a solid state metathesis reaction. All the materials were characterized by powder X-ray diffraction (XRD) and infrared spectroscopy (IR). These metal doped diphosphates were crystallized in a tetragonal lattice with space group P42/mnm. The IR spectra of all the samples were characterized by bands due to the P2O74- group. The powder electron spin resonance (ESR) spectrum of Na1.88Gd0.04ZnP2O7 gave a characteristic “U” type spectrum. The powder ESR spectrum of Na1.92Mn0.04ZnP2O7 consists of six lines while Na1.92Cu0.04ZnP2O7 gave a broad profile. All the doped metal ions occupy the Na+ site in the diphosphate lattice. The broad emission band at 614 nm (red band) observed for Na1.92Mn0.04ZnP2O7 is assigned to an electronic transition T14(G4)→A16(S6) of Mn2+ in distorted octahedral coordination.

  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 and TL studies of irradiated Anatolian laurel leaf (Laurus nobilis L.)

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

    Laurel leaf (Laurus nobilis L.) samples that originated from Turkey were analyzed by electron spin resonance (ESR) and thermoluminescence (TL) techniques before and after γ-irradiation. Unirradiated (control) laurel leaf samples exhibit a weak ESR singlet centered at g=2.0020. Besides this central signal were two weak satellite signals situated about 3 mT left and right to it in radiation-induced spectra. The dose-response curve of the radiation-induced ESR signal at g=2.0187 (the left satellite signal) was found to be described well by a power function. Variation of the left satellite ESR signal intensity of irradiated samples at room temperature with time in a long term showed that cellulosic free radicals responsible for the ESR spectrum of laurel leaves were not stable but detectable even after 100 days. Annealing studies at four different temperatures were used to determine the kinetic behavior and activation energy of the radiation-induced cellulosic free radicals responsible from the left satellite signal (g=2.0187) in laurel leaves. TL measurements of the polymineral dust isolated from the laurel leaf samples allowed distinguishing between irradiated and unirradiated samples.

  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.

  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. [Study of the state of mitochondria at low temperatures by the ESR method].

    PubMed

    Nardid, O A; Zagnoĭko, V I; Moiseev, V A; Lugovoĭ, V I

    1984-01-01

    Possible usage of ESR probe method for studying low temperature effect on structural and functional state of mitochondria is under study. It is shown that during freezing out of mitochondrial water there is sharp dehydration of intermitochondrial matrix and membrane thickening. The facts are given about damage of barrier function of the membrane at the moment of appearance of extramitochondrial liquid phase during thawing.

  13. 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...

  14. Screening of free radical formation in crystals of guanosine by ESR study

    NASA Astrophysics Data System (ADS)

    Usta, Ayhan; Vural, Hasibe Cingilli; Asik, Biray; Usta, Keziban

    2011-10-01

    In this study, to obtain guanosine polycrystalline, novel crystallization method was performed on powder guanosine material. Effective crystallization conditions were achieved by adjustment of the concentration of the metal ions, chemical solutions, NaCl, KCl, glacial acetic acid, nitric oxide, perchloric acid, glutamic acid, and pH of buffer. Behaviors of the guanosine polycrystal samples exposed to high-energy values were investigated using ESR method. The polycrystal samples were exposed to gamma-rays for 48 and 72 h. ESR signals were not recorded from the non-irradiated sample and the sample irradiated for 48 h, but the polycrystalline sample irradiated for 72 h exhibited complex ESR spectra. ESR measurements were taken on the irradiated sample in temperature range from 300 to 450 K. On the basis of all these measurements dependence temperature, it can be said that the shape of the spectrum was to be dependent on temperature slightly. Hence, we assume that the radical structure occurred was resistance to high temperature. Two radicals were determined in the structure irradiated and these were called radical I and radical II. The g, hyperfine constants, and spin density were found to be ρ = 0.96, a=2.7 mT, a=1.155 mT, aN = 0.35 mT and g1 = 2.0093 for the radical I; aN = 4.7 mT and g2 = 2.0094 for the radical II.

  15. 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

  16. Acid-catalysed autoreduction of ferrylmyoblobin in aqueous solution studied by freeze quenching and ESR spectroscopy.

    PubMed

    Kröger-Ohlsen, M V; Andersen, M L; Skibsted, L H

    1999-04-01

    Decay of the hypervalent muscle pigment ferrylmyoglobin, formed by activation of metmyoglobin by hydrogen peroxide, was found, when studied by a combination of ESR and UV/VIS spectroscopy in aqueous solution at physiological pH, to proceed by parallel second- and first-order kinetics. At pH below 6.5 a sharp ESR signal (g = 2.003) with an increasing intensity for decreasing pH were observed in solutions frozen in liquid nitrogen, and a broad signal (g = 2.005) was seen throughout the studied pH range also in frozen solutions. The g = 2.005 signal is suggested to arise from an intermediate formed in an intramolecular rate-determining electron-transfer in ferrylmyoglobin, whereas the g 2.003 signal is caused by a radical formed in a proton-assisted electron-transfer initiating the specific acid-catalysed autoreduction.

  17. 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.

  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. Spin-probe ESR and molecular modeling studies on calcium carbonate dispersions in overbased detergent additives.

    PubMed

    Montanari, Luciano; Frigerio, Francesco

    2010-08-15

    Oil-soluble calcium carbonate colloids are used as detergent additives in lubricating oils. They are colloidal dispersions of calcium carbonate particles stabilized by different surfactants; in this study alkyl-aryl-sulfonates and sulfurized alkyl-phenates, widely used in the synthesis of these additives, are considered. The physical properties of surfactant layers surrounding the surfaces of calcium carbonate particles were analyzed by using some nitroxide spin-probes (stable free radicals) and observing the corresponding ESR spectra. The spin-probe molecules contain polar groups which tend to tether them to the carbonate particle polar surface. They can reach these surfaces only if the surfactant layers are not very compact, hence the relative amounts of spin-probe molecules accessing carbonate surfaces are an index of the compactness of surfactant core. ESR signals of spin-probe molecules dissolved in oil or "locked" near the carbonate surfaces are different because of the different molecular mobility. Through deconvolution of the ESR spectra, the fraction of spin-probes penetrating surfactant shells have been calculated, and differences were observed according to the surfactant molecular structures. Moreover, by using specially labeled spin-probes based on stearic acids, functionalized at different separations from the carboxylic acid group, it was possible to interrogate the molecular physical behavior of surfactant shells at different distances from carbonate surfaces. Molecular modeling was applied to generate some three-dimensional micellar models of the colloidal stabilizations of the stabilized carbonate particles with different molecular structures of the surfactant. The diffusion of spin-probe molecules into the surfactant shells were studied by applying a starting force to push the molecules towards the carbonate surfaces and then observing the ensuing behavior. The simulations are in accordance with the ESR data and show that the geometrical

  20. Magnetic anisotropy of copper(II) complxes from ESR studies in solution. Use of mixed ligand complexes

    NASA Astrophysics Data System (ADS)

    Das, Ranjan; Prabhananda, B. S.

    ESR linewidhts of the complex Cu(Q) 2 and that of the mixed ligand complx Cu(P)(Q) in liquid solution, where P and Q are two different ligand groups, can be used to determine or confirm the anisotropy of Cu(Q) 2, when the anisotropy parameters associated with Cu(P) 2 are known. This method makes use of (i) the equations derived by Kivelson and coworkers (Wilson and Kivelson, J. Chem. Phys., 44, 154 (1966) ; Atkins and Kivelson, J. Che. Phys., 44, 169 (1966)) ; (ii) equations which find justification in the model proposed by Kuska and coworkers (Kuska, Rogers, and Drullinger, J. Phys. Chem., 71, 109 (1967) ; Kuska, J. Am. Chem. Soc., 97, 2289 (1975)) to explain the variation of metal hyperfine constant. Our proecedure is shown to be promising by taking the example of Cu {i-C 3H 7O) 2PSe 2} 2. This method could be useful when it is difficult to obtain good frozen solution/single crystal ESR spectra.

  1. Q-band studies of the ESR signal in tooth enamel

    NASA Astrophysics Data System (ADS)

    Skinner, Anne R.; Dennis Chasteen, N.; Shao, Junlong; Blackwell, Bonnie A. B.

    2001-12-01

    Tooth enamel is one of the most promising materials for electron spin resonance (ESR) dating because the X-band signal is large, easy to measure, and extremely stable. The mean lifetime at ambient temperature has been measured greater than the age of the Earth! However, the X-band spectrum in fossil teeth is, in fact, a composite of two signals that can be resolved if the sample is examined in the Q-band region. The relative size of the two signals appears to be a function of degree of fossilization; older teeth have a better-defined second signal. A study of the dependence of these signals on radiation dose, microwave power, and temperature strongly suggests that both signals are located in the hydroxyapatite crystal structures. As such, then, the X-band spectrum, measured at moderate modulation amplitude, is suitable for determining the age of fossil teeth.

  2. ESR ST study of hydroxyl radical generation in wet peroxide system catalyzed by heterogeneous ruthenium.

    PubMed

    Rokhina, Ekaterina V; Golovina, Elena A; As, Henk van; Virkutyte, Jurate

    2009-09-01

    Ru-based catalysts gained popularity because of their applicability for a variety of processes, including carbon monoxide oxidation, wet air catalytic oxidation and wastewater treatment. The focus of a current study was generation of hydroxyl radicals in the wet peroxide system catalyzed by heterogeneous ruthenium, spin-trapped by DEPMPO and DIPPMPO by means of electron spin resonance spin-trapping technique (ESR ST). The mechanism of free radicals formation was proposed via direct cleavage of hydrogen peroxide over ruthenium active sites. The chemical reactions occurring in the system were introduced according to the experimental results. Also, radical production rate was assessed based on concentration changes of species involved in the bulk liquid phase oxidation.

  3. Electrochemical and esr spin trap studies of a new iron tetra-catecholamide complex.

    PubMed

    Cheraïti, N; Brik, M E; Keita, B; Nadjo, L; Gaudemer, A

    1999-08-16

    A new siderophore, N5,N6-thiodipropanoyl-bis[N1,N10-bis(2,3-dihydroxy benzoyl-spermidine)]-Fe (III) complex or H2LFe has been synthesised. The reaction of the reduced form of this complex with dioxygen has been investigated through electrochemical study and revealed the formation of a new species assumed to be H2O2. This species has been confirmed by esr spectroscopy using the diamagnetic compound 5-deutero-2,2,5-trimethylpyrrolidine-1-hydroxyl as spin trap. The resulting persistent radical is 5-deutero-2,2,5-trimethylpyrrolidine-1-yloxy (aN = 16.58 G, aD = 3.49 G).

  4. ESR study on the antioxidant activity of TAK-218 in biological model membranes.

    PubMed

    Murakami, M; Fukatsu, K; Ohkawa, S; Kasahara, F; Sugawara, T

    2000-06-01

    TAK-218 has a 2,3-dihydrobenzofuran-5-amine (coumaran) structure which resembles alpha-tocopherol, and is a promising candidate as an agent for central nervous system (CNS) trauma and ischemia. The radical scavenging activity of TAK-218 was studied using electron spin resonance (ESR) spectroscopy. TAK-218 exhibited a more potent scavenging activity towards the hydroxyl radical than did the well-known hydroxyl radical scavengers, mannitol and dimethylsulfoxide. Towards the superoxide radical, TAK-218 showed equal potency to glutathione. TAK-218 reacted rapidly with stable radicals, such as galvinoxyl and 2,2-diphenyl-1-picrylhydrazyl hydrate (DPPH), and gave the quinone as a two-electron oxidized product in analogy with alpha-tocopherol. To exhibit an excellent antioxidative activity in living systems, the compounds should not only have the intrinsic radical scavenging activity but also good distribution in the biological lipid-bilayer membrane. To examine the antioxidant activity of TAK-218, the inhibition of lipid peroxidation by alpha-tocopherol and TAK-218 in liposomal membranes was studied using an ESR spin-label technique. Both alpha-tocopherol and TAK-218 completely inhibited lipid peroxidation by radicals generated in an aqueous layer using a water-soluble radical initiator, 2,2'-azobis-(2-amidinopropane) hydrochloride (AAPH). At a high incubation temperature (45 degrees C), alpha-tocopherol scavenged radicals more effectively than TAK-218 on the surface of the membrane, while TAK-218 scavenged radicals more effectively in the interior of the membrane. The difference between TAK-218 and alpha-tocopherol for radical scavenging in the membrane system derives from the different distribution pattern of these compounds. TAK-218 can penetrate the membrane freely and can scavenge the radical in the membrane interior. Furthermore, TAK-218 was shown to inhibit lipid peroxidation initiated by a lipid soluble radical initiator, 2,2'-azobis-(2,4-dimethylvaleronitrile

  5. Study of the ESR signal of gamma irradiated hydroxyapatite for dose assessment

    NASA Astrophysics Data System (ADS)

    Da Costa, Z. M.; Pontuschka, W. M.; Campos, L. L.

    2004-06-01

    In this work the ESR signal based on the measurement of the concentration of radiation induced radicals CO 2- in hydroxyapatite, obtained from human tooth enamel, was investigated aiming to standardise the sample preparation method and the measurement conditions for practical application of this technique to accident personal dosimetry. In this regard, practical considerations of sample preparation, grain size, ESR spectrum, spurious induced mechanical ESR signal, influence of dose radiation and measurement temperatures are discussed, as well are presented results of signal reproducibility, angular and microwave power signal dependence.

  6. ESR study of some sulfur-centered radicals formed in irradiated cysteamine and 1,4-dithiane single crystals

    SciTech Connect

    Bonazzola, L.; Fackir, L.; Leary, N.; Roncin, J.

    1984-03-01

    Cysteamine and 1,4-dithiane single crystals have been exposed to /sup 60/Co ..gamma.. rays or irradiated with ultraviolet light. The main sulfur-centered radicals are assigned as RCH/sub 2/S and RCH/sub 2/SS from the comparative study by ESR of the hyperfine couping and of the g tensors.

  7. 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

  8. Order and dynamics inside H-PDLC nanodroplets: an ESR spin probe study.

    PubMed

    Bacchiocchi, Corrado; Miglioli, Isabella; Arcioni, Alberto; Vecchi, Ilaria; Rai, Kashma; Fontecchio, Adam; Zannoni, Claudio

    2009-04-23

    We have performed a detailed study of the order and dynamics of the commercially available BL038 liquid crystal (LC) inside nanosized (50-300 nm) droplets of a reflection-mode holographic-polymer dispersed liquid crystal (H-PDLC) device where LC nanodroplet layers and polymer layers are alternately arranged, forming a diffraction grating. We have determined the configuration of the LC local director and derived a model of the nanodroplet organization inside the layers. To achieve this, we have taken advantage of the high sensitivity of the ESR spin probe technique to study a series of temperatures ranging from the nematic to the isotropic phase of the LC. Using also additional information on the nanodroplet size and shape distribution provided by SEM images of the H-PDLC cross section, the observed director configuration has been modeled as a bidimensional distribution of elongated nanodroplets whose long axis is, on the average, parallel to the layers and whose internal director configuration is a uniaxial quasi-monodomain aligned along the nanodroplet long axis. Interestingly, at room temperature the molecules tend to keep their average orientation even when the layers are perpendicular to the magnetic field, suggesting that the molecular organization is dictated mainly by the confinement. This result might explain, at least in part, (i) the need for switching voltages significantly higher and (ii) the observed faster turn-off times in H-PDLCs compared to standard PDLC devices.

  9. ESR and mass-spectrometric uranium-series dating studies of a mammoth tooth from stanton harcourt, Oxfordshire, England

    NASA Astrophysics Data System (ADS)

    Zhou, L. P.; McDermott, F.; Rhodes, E. J.; Marseglia, E. A.; Mellars, P. A.

    The age of the Channel Deposits at Stanton Harcourt, Oxfordshire, England, has been a topic of debate with important implications for British Pleistocene stratigraphy. Recent excavations led by K. Scott reveal ample evidence for ancient environmental conditions characteristic of an interglacial. However, the question remains on the assignment of its age. At present it is thought to represent an interglacial corresponding to either marine OI Stage 7 or 5e. In an attempt to constrain the chronology of the site, and to assess the techniques' reliability, we have made electron spin resonance (ESR) measurements on enamel and mass-spectrometric U-series measurements on both enamel and dentine from a mammoth tooth buried in the Channel Deposits at Stanton Harcourt. Four dentine samples gave U-series dates between 65.4±0.4 and 146.5±1.0 ka and two enamel samples between these dentine layers were dated to 53.3±0.2 and 61.1±0.6 ka. The corresponding ESR age estimates for the enamel samples are 59±6 and 62±4 ka (early U-uptake, EU) and 95±11 and 98±7 ka (linear U-uptake, LU). The recent U-uptake (RU) dates are 245±38 and 238±31 ka, but in light of the U-series data we would not expect these to represent realistic age estimates. Similar ESR results were obtained from two other adjacent enamel samples. The effect of the large size of the mammoth tooth on the external gamma dose, and the internal gamma contribution from the high U content of the dentine, are considered. While the recent uptake ESR dates appear to coincide with OI Stage 7, all the early and linear uptake ESR and mass-spectrometric U-series dates are younger than the expected age estimation based on recent geological interpretation and amino acid racemisation measurements (>200 ka) and optical dating studies (200-450 ka). Possible causes of the unexpected dating results are discussed. We conclude that our mass-spectrometric U-series and EU and LU ESR measurements represent minimum age estimates for the

  10. Theoretical studies of diatomic and triatomic systems containing the group IB atoms Cu, Ag, and Au

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1986-01-01

    Selected portions of the ground state potential energy surfaces of the Cu3, Ag3, AgCu2, and AuCu2 trimers are studied at the single-reference singles plus doubles configuration interaction and couple pair functional levels correlating 33 electrons. The calculations use the effective core potentials of Hay and Wadt (1985) to replace the deep core levels. The Cu3 and Ag3 molecules are found to have 2B2 obtuse-angled ground states, with low-lying 2A1 acute-angled excited states. The AgCu2 and AuCu2 molecules have 2A1 acute-angled ground states. The Cu3 molecule has a smaller 3d population than Ag3, and Cu3 has a smaller s electron density in the open-shell orbital than does Ag3, in agreement with recent ESR experiments.

  11. Study on ESR and inter-related properties of vacuum-dehydrated nanotubed titanic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Shunli; Li, Wei; Jin, Zhensheng; Yang, Jianjun; Zhang, Jingwei; Du, Zuliang; Zhang, Zhijun

    2004-04-01

    Nanotubed titanic acid (H 2Ti 2O 4(OH) 2) is a novel kind of material. The electron spin resonance (ESR) and inter-related properties of its vacuum-dehydrated product were investigated by means of transmission electron microscopic, X-ray diffraction, ESR, diffuse reflectance spectra. The results showed that after treatment under vacuum (-0.1 MPa) at 100°C, single-electron-trapped oxygen vacancies (SETOV), characterized by a symmetrical ESR signal ( g=2.003), were generated in nanotubed H 2Ti 2O 4(OH) 2 crystal lattice. The g=2.003 ESR signal intensity ( IESR) increased with treatment time. SETOV played the role of F centers, the visible-light absorption power of vacuum-dehydrated H 2Ti 2O 4(OH) 2 was proportional to IESR. During vacuum dehydration at 100°C, the H 2Ti 2O 4(OH) 2 nanotubes shortened but its crystalline form kept unchanged. The formation mechanism of SETOV was discussed.

  12. Study of Single-Power, Two-Circuit ESR Process with Current-Carrying Mold: Development of the Technique and Its Physical Simulation

    NASA Astrophysics Data System (ADS)

    Dong, Yanwu; Jiang, Zhouhua; Cao, Haibo; Hou, Zhiwen; Yao, Kean

    2016-12-01

    Physical simulation of a single-power, two-circuit electroslag remelting (ESR) process with current conductive mold (ESR-STCCM) is carried out in this paper. Wood alloy and sodium chloride solution are used to study the current distribution ratio of passing electrode and conductive part of current carrying mold (conductor). A conventional ESR (CESR) process has been studied as a comparison. The total current of ESR-STCCM is larger than the CESR process, which indicates that the resistance in ESR-STCCM is smaller than in CESR. Results show that the ratio of I electrode/ I conductor changes with filling ratio, electrode immersion depth, and effective conductor height. Electrode immersion depth plays an important role on the current distribution ratio. Nevertheless, the effective conductor height has a little influence on the current distribution ratio. A larger filling ratio has an obvious effect on the current distribution ratio in ESR-STCCM. Current flowing through the electrode increases with the increasing of electrode immersion depth under a certain filling ratio. The physical model established can provide an important direction to real ESR-STCCM.

  13. Copper (II) complexes of N4, N4-disubstituted thio- and selenosemicarbazones of 2-acetylpyridine: ESR studies

    NASA Astrophysics Data System (ADS)

    K. Bhoon, Yudhvir; Scovill, John P.; Klayman, Daniel L.

    Copper(II) complexes of 3-azabicyclo[3.2.2]nonane-3-thiocarboxylic acid 2-[1-(pyridinyl)ethylidene]hydrazide, and its selenium analog, 3-azabicyclo[3.2.2]nonane-3-selenocarboxylic acid 2-[1-(2-pyridinyl)ethylidene]hydrazide, were studied by ESR spectrometry in chloroform solution at room temperature and at liquid nitrogen temperature. ESR spectra were also observed for the complexes as magnetically doped samples in the corresponding Ni(II) lattices at room temperature. Nitrogen superhyperfine splitting is observed at room temperature in all the spectra. Splitting patterns indicate the non-equivalent nature of the two coordinating nitrogen atoms. The covalency parameter for the metal—ligand bond was determined for selected complexes. An order of ligand field strength has been proposed based on the magnitude of the g| component of g observed in the polycrystalline state.

  14. 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.

  15. 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.

  16. 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).

  17. ESR study on radiation-induced radicals in carboxymethyl cellulose aqueous solution

    NASA Astrophysics Data System (ADS)

    Saiki, Seiichi; Nagasawa, Naotsugu; Hiroki, Akihiro; Morishita, Norio; Tamada, Masao; Kudo, Hisaaki; Katsumura, Yosuke

    2011-02-01

    Carboxymethyl cellulose (CMC) at highly concentrated aqueous solution undergoes radiation crosslinking reaction by ionizing irradiation. It is assumed that this radiation-induced reaction takes place by the indirect effect of water radiolysis, especially through the OH radical. However, the reaction mechanism is not well known. In this topic, ESR spectra of CMC radicals formed by reaction with OH radicals were measured directly in aqueous solution to identify the initially formed radical site. The ESR spectra were observed successfully and were interpreted as the overlapping of two spectra; a Triplet×Doublet spectrum and a Doublet spectrum. Each spectrum was assigned to radicals located on carboxymethyl groups linked to C6 and C2/C3.

  18. Cu(II) complexes in bacterial growth medium: electron spin resonance study

    NASA Astrophysics Data System (ADS)

    Jung, Katinka; Ristori, Sandra; Martini, Giacomo

    2000-02-01

    In this study we report a spectroscopic investigation on the structure and stability of Cu(II)-complexes that are formed in a minimum growth medium (MM), normally used for Bacillus subtilis cultures. As other transition metals, Cu(II) compounds are toxic to this bacterium and the toxicity depends on the Cu(II) concentration. MM contained NH 4+ ions and asparagine (asn) as the source of inorganic and organic nitrogen. Both ESR and electronic spectra demonstrated the very important role played by the amino acid asparagine in the coordinative behaviour of Cu(II). In particular, three different complexes were evidenced: Cu(H 2O) 62+; Cu(asn) + and Cu(asn) 2. The relative amount of these three species strongly depended on pH, on Cu:asn ratio and on the presence of the phosphate ions. They were identified and evaluated quantitatively by extensive simulation of the electron spin resonance (ESR) spectra recorded in different experimental conditions. The bis-complex was found to be more stable in MM than in an asparagine-containing water solution with the same Cu:asn ratio. A comparison of the spectroscopic results with microbiological investigations is also made.

  19. 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.

  20. ESR study of p-type natural 2H-polytype MoS2 crystals: The As acceptor activity

    NASA Astrophysics Data System (ADS)

    Stesmans, A.; Iacovo, S.; Afanas'ev, V. V.

    2016-10-01

    Low-temperature (T = 1.7-77 K) multi frequency electron spin resonance (ESR) study on p-type 2H-polytype geological MoS2 crystals reveals p-type doping predominantly originating from As atoms substituting for S sites in densities of (2.4 ± 0.2) × 1017 cm-3. Observation of a "half field"(g ˜ 3.88) signal firmly correlating with the central Zeeman As accepter signal indicates the presence of spin S > ½ As agglomerates, which together with the distinct multicomponent makeup of the Zeeman signal points to manifest non-uniform As doping; only ˜13% of the total As response originates from individual decoupled As dopants. From ESR monitoring the latter vs. T, an activation energy Ea = (0.7 ± 0.2) meV is obtained. This unveils As as a noticeable shallow acceptor dopant, appropriate for realization of effective p-type doping in targeted 2D MoS2-based switching devices.

  1. Dynamic crossovers and activated regimes in a narrow distribution poly(n-butyl acrylate): an ESR study

    NASA Astrophysics Data System (ADS)

    Andreozzi, Laura; Autiero, Ciro; Faetti, Massimo; Giordano, Marco; Zulli, Fabio

    2006-07-01

    The rotational dynamics of the spin probe cholestane dissolved in a narrow distribution poly(n-butyl acrylate) sample has been investigated via electron spin resonance (ESR) spectroscopy. The measurements were carried out in a wide temperature range: different dynamic regions have been recognized, and the coupling of the probe dynamics to the α and secondary relaxations has been revealed. In particular, the coupling with the structural relaxation is ruled by two fractionary Vogel-Fulcher laws (VF). The crossover from one VF region to the other occurs at the temperature TC = 1.17Tg, signalling the onset of the cooperativity in the dynamics and confirming a behaviour previously observed in ESR studies carried out on polymeric glass-formers. Furthermore, in this work we discuss the activated regime at the highest temperatures and show that the activation energy does not depend on the length of the polymer main- and side-chains, while its onset temperature linearly depends on the chain length.

  2. Preliminary study of FMO1, FMO5, CYP21, ESR1, PLIN2 and SULT2A1 as candidate gene for compounds related to boar taint.

    PubMed

    Neuhoff, Christiane; Gunawan, Asep; Farooq, Malik Omar; Cinar, Mehmet Ulas; Große-Brinkhaus, Christine; Sahadevan, Sudeep; Frieden, Luc; Tesfaye, Dawit; Tholen, Ernst; Looft, Christian; Schellander, Karl; Uddin, Muhammad Jasim

    2015-10-01

    An association study between polymorphisms of six genes and boar taint related compounds androstenone, skatole and indole was performed in a boar population (n=370). Significant association (P<0.05) was detected for SNP of FMO5 (g.494A>G) with all boar taint compounds, SNP of CYP21 (g.3911T>C) with skatole and indole, and SNP of ESR1 (g.672C>T) with androstenone and indole. mRNA expression of CYP21 and ESR1 was higher in CAB (castrated boar) compared to non-castrated boars; whereas, the expression of FMO5 and ESR1 was higher in LBT (low boar taint) compared to HBT (high boar taint) in liver tissue. FMO5, CYP21 and ESR1 proteins were less detectable in HBT compared with LBT and CAB in liver tissues. These findings suggest that FMO5, CYP21 and ESR1 gene variants might have effects on the boar taint compounds.

  3. Association study and expression analysis of porcine ESR1 as a candidate gene for boar fertility and sperm quality.

    PubMed

    Gunawan, Asep; Kaewmala, Kanokwan; Uddin, Muhammad Jasim; Cinar, Mehmet Ulas; Tesfaye, Dawit; Phatsara, Chirawath; Tholen, Ernst; Looft, Christian; Schellander, Karl

    2011-10-01

    Male fertility is impaired through the lack of ESR1 (Estrogen Receptor 1) but little is known about the ESR1 roles in boar spermatogenesis and fertility. Therefore, this research was aimed at investigating the association with sperm quality and boar fertility traits in a total of 300 boars both from purebred Pietrain and Pietrain × Hampshire crosses. A SNP in coding region of ESR1g.672C>T in exon 1 was associated with sperm motility (P<0.05) and plasma droplet rate (P<0.01) while the polymorphism in non-coding region of ESR1g.35756T>C in inton 1 was associated with non-return rate (P<0.05). Furthermore, to analyse the mRNA and protein expression of ESR1 in boar reproductive tissues, a total of six boars were divided into two groups [Group I (G-I) and Group II (G-II)], where G-I had relatively better sperm quality. ESR1 expression was higher in tissues collected from G-I boars than those of collected from G-II boars, and the difference in mRNA expression was significant (P<0.01) in head of epididymis. The ESR1 protein expression results from western blot coincided with the results of qRT-PCR. The ESR1 protein localization observed a strong staining in the cytoplasm of Sertoli cell in the testis, in the epithelial cells in head and tail of epididymis, in smooth muscle in tail of epididymis, and in the post acrosomal region and tail of the spermatozoa. These results will improve the understanding of the functions of the ESR1 in spermatogenesis within the reproductive tract and will shed light on ESR1 as a candidate in the selection of boar with good sperm quality and fertility.

  4. An ESR study of the nitroxide radical of pentastarch-conjugated deferoxamine

    SciTech Connect

    Pieper, G.M.; Gross, G.J.; Kalyanaraman, B. )

    1990-01-01

    At higher concentrations, deferoxamine (DFO) reacts with hydroxyl radicals to produce a stable nitroxide free radical. Formation and decay of this nitroxide radical was investigated and compared with a novel modified pentastarch conjugate of DFO (MPS-DFO). Photolytic generation of hydroxyl radicals from H2O2 in the presence of free DFO produced a nitroxide radical with coupling constants of aN = 8.0 G and aH = 6.5 G. Under the same experimental conditions, equimolar concentrations of MPS-DFO produced an ESR signal of reduced intensity while iron-saturated MPS-DFO produced no signal. Incubation of free DFO with pentastarch (i.e., without conjugation) greatly decreased the intensity of the nitroxide radical signal. Using a spin-trapping technique with 5,5-dimethyl-1-pyrroline N-oxide (DMPO), the pentastarch vehicle was shown to inhibit the DMPO-OH adduct formation. The decay of the DFO nitroxide radical decayed with a second-order rate constant while that of MPS-DFO decayed with a first-order rate constant. Thus, a novel derivative of DFO may provide some additional benefit in limiting DFO nitroxide radical formation and might explain the reported reduced in vivo toxicity of MPS-DFO relative to free DFO.

  5. 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.

  6. 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.

  7. ESR spectrometer with a loop-gap resonator for cw and time resolved studies in a superconducting magnet.

    PubMed

    Simon, Ferenc; Murányi, Ferenc

    2005-04-01

    The design and performance of an electron spin resonance spectrometer operating at 3 and 9 GHz microwave frequencies combined with a 9-T superconducting magnet are described. The probehead contains a compact two-loop, one gap resonator, and is inside the variable temperature insert of the magnet enabling measurements in the 0-9T magnetic field and 1.5-400 K temperature range. The spectrometer allows studies on systems where resonance occurs at fields far above the g approximately 2 paramagnetic condition such as in antiferromagnets. The low quality factor of the resonator allows time resolved experiments such as, e.g., longitudinally detected ESR. We demonstrate the performance of the spectrometer on the NaNiO2 antiferromagnet, the MgB2 superconductor, and the RbC60 conducting alkaline fulleride polymer.

  8. Photochemical synthesis of simple organic free radicals on simulated planteary surfaces-an ESR study.

    PubMed

    Tseng, S S; Chang, S

    1975-01-01

    Electron spin resonance spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170C 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 absorbed on silica gel at -170C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, re-irradiation 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 which 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 by means of (1) photodissociation of H2O physically adsorbed on the silica gel, or (2) absorption of the excitation energy by the silica gel surface with subsequent cleavage of the silanol bonds, or (3) dissociation of H2O molecules throug photosensitization by the surfaces or a combination of (1) to (3). Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precsursors of formic acid. Our 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.

  9. ESR study of the radiolysis of cellobiose, cellulose-containing materials, and their mixtures with methyl methacrylate

    SciTech Connect

    Kozlova, E.Y.; Shostenko, A.G.; Ermolaev, S.V.

    1995-01-01

    The ESR spectra of {gamma}-irradiated cellobiose, paper waste, and cellulose extracted from paper waste and waste pulp sludge were analyzed. The kinetics of formation and decay of cellobiose radicals were investigated, and the radiation-chemical yields of the radicals formed in cellulose-containing materials were calculated. The ESR spectra of cellobiose irradiated in the presence of methyl methacrylate (MMA) were obtained. A probable mechanism of MMA grafting onto cellulose-containing matrices is considered.

  10. Vanadyl-Induced Fenton-Like Reaction in RNA. An ESR and Spin Trapping Study

    DTIC Science & Technology

    1990-02-01

    reactions in terest in biology. Similar to Fe(II) and Cu( l ), VO 2, par- RNA. Spin trapping is a technique by which a short- ticipates in Fenton-like...in a separating funnel, water obtained from a Sybron/Barn- in the presence of D, L -histidine (I x 10- 2 M) and the stead NANO pure system with a 0.001...DIIC EL1"&7 C -JOPY Form ApprovedREPORT DOCUMENTATION PAGE 0MB No. 0704-01788 Pubisc rSeodirtflW burden for 10rit collecion of inomto a mirrolved to

  11. ESR and magnetization studies of Fe2O3-Bi2O3-ZnO-PbO glass system

    NASA Astrophysics Data System (ADS)

    Pelluri, Sandhya Rani; Singh, Rajender

    2016-11-01

    The electron spin resonance (ESR) and magnetization measurements were undertaken to understand the magnetic phenomena in the glass system with composition (Fe2O3)x (70 Bi2O3 20 ZnO 10 PbO)1-x (x=15, 20 and 25 mol%). At high temperature the ESR spectra consists of narrow resonance at g~2. As the temperature decreases a second resonance peak emerges and with further decrease in temperature, the second resonance peak progressively shifts towards lower field value. The ESR data shows the formation of superparamagnetic clusters. The temperature dependent magnetization data exhibits a spin glass-like transition and a superparamagnetic blocking at a temperature which increases with increase in x value.

  12. Magnetic, electronic and electrochemical studies of mono and binuclear Cu(II) complexes using novel macrocyclic ligands.

    PubMed

    Gupta, Nidhi; Gupta, Rachna; Chandra, Sulekh; Bawa, S S

    2005-04-01

    A series of new mono and binuclear copper (II) complexes [Cul]X(2)and [Cu(2)lX(2)] where 1 = L(1), L(2) and L(3) are the macrocyclic ligands. In mononuclear complexes the geometry of Cu(II) ion is distorted squareplanar and in binuclear complexes the geometry of Cu(II) is tetragonal. The synthesized complexes were characterized by spectroscopic (IR,UV-vis and ESR) techniques. Electrochemical studies of the complexes reveals that all the mononuclear Cu(II) complexes show a single quasireversible one-electron transfer reduction wave (E(pc) = -0.76 to -0.84V) and the binuclear complexes show two quasireversible one electron transfer reduction waves (E(pc)(1) = -0.86 to -1.01V, E(pc)(2) = -1.11 to -1.43V) in cathodic region. The ESR spectra of mononuclear complexes show four lines with nuclear hyperfine splittings with the observed g(11) values in the ranges 2.20-2.28, g( perpendicular) = 2.01-2.06 and A(11) = 125-273. The binuclear complexes show a broad ESR spectra with g = 2.10-2.11. The room temperature magnetic moment values for the mononuclear complexes are in the range [mu(eff) = 1.70-1.72BM] and for the binuclear complexes the range is [mu(eff) = 1.46-1.59BM].

  13. ESR study of photoinduced free radicals by visible light in hair and the effects of ascorbic acid (vitamin C).

    PubMed

    Chikvaidze, E; Khachatryan, I

    2011-08-01

    The ESR spectra of melanin's free radicals in natural black and red hair have been investigated. It is shown that the ESR spectrum of black hair is slightly asymmetric singlet with g=2.0037 and ΔH=0.5 mTl. The ESR spectrum of red hair with g=2.0053 differs from the spectrum of black hair. Using the method of saturation was shown that ESR spectrum of red hair represents a superposition of two signals: a singlet, relating to the black hair, and a triplet from red hair's pheomelanin. Under the influence of visible light (blue with λ(max) =450 nm, green with λ(max) =510 nm and red with λ(max) =650 nm) in both types of hair (black and red), the photoinduced free radicals appear, which indicates an increase in the intensity of already existing ESR spectrum of hair. It should be noted that the ESR spectra of red hair from various donors are different. The antioxidant ascorbic acid (vitamin C) has the different effect on the photoinduced free radicals. In particular, in the case of black hair, the concentration of photoinduced free radicals is slightly reduced, whereas in red hair, the disappearance of the triplet in the spectrum is observed, and at the same time, the spectrum becomes a singlet, the intensity of which increases sharply. It is assumed that the antioxidants, effective for black hair, may be ineffective for red hair and vice versa. Therefore, in each, specific case is necessary to investigate the effectiveness of an antioxidant separately.

  14. 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.

  15. The influence of tin compounds on the dynamic properties of liposome membranes: a study using the ESR method.

    PubMed

    Man, Dariusz; Podolak, Marian; Engel, Grzegorz

    2006-01-01

    The influence of organic and inorganic compounds of tin on the dynamic properties of liposome membranes obtained in the process of dipalmitoylphosphatidylcholine (DPPC) sonication in distilled water was investigated. This was carried out by means of the spin ESR probe method. The probes were selected in such a way as to penetrate different areas of the membrane (a TEMPO probe, 5-DOXYL stearic acid, 16-DOXYL stearic acid). Four compounds of tin were chosen: three organic ones, (CH(3))(4)Sn, (C(2)H(5))(4)Sn and (C(3)H(7))(3)SnCl, and one inorganic one, SnCl(2). The investigated compounds were added to a liposome dispersion, which was prepared prior to that. The concentration of the admixture was changed within the values from 0 to 10%-mole in proportion to DPPC. The studies indicated that the chlorides of tin display the highest activity in their interaction with liposome membranes. Since these compounds have ionic form in a water solution, the obtained result can mean that this form of admixture has a considerable influence on its activity. Furthermore, it was found that there is a slightly stronger influence of tin compounds with a longer hydrocarbon chain on changes in the probes' spectroscopic parameters.

  16. Direct observation of hexamethylbenzenium radical cations generated during zeolite methanol-to-olefin catalysis: an ESR study.

    PubMed

    Kim, Sun Jung; Jang, Hoi-Gu; Lee, Jun Kyu; Min, Hyung-Ki; Hong, Suk Bong; Seo, Gon

    2011-09-07

    The generation of hexamethylbenzenium radical cations as the key reaction intermediate in chabazite-type molecular sieve acids (i.e., H-SAPO-34 and H-SSZ-13) during the methanol-to-olefin process has been directly evidenced by ESR spectroscopy.

  17. 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)

  18. LC/ESR/MS study of pH-dependent radical generation from 15-LOX catalyzed DPA peroxidation

    PubMed Central

    Purwaha, Preeti; Gu, Yan; Kelavkar, Uddhav; Kang, Jing Xuan; Law, Benedict; Wu, Erxi; Qian, Steven Y.

    2011-01-01

    Docosapentaenoic acid (DPA) is a unique fatty acid that exists in two isomeric forms (n-3 and n-6) which differ in their physiological behaviors. DPA can undergo free-radical mediated peroxidation via lipoxygenase (LOX). 15-LOX, one of the LOX isomers, has received much attention in cancer research due to its very different expression level in normal tissues compared to tumors and some bioactive fatty acid metabolites modulating the tumorigenic pathways in cancer. However, the mechanism linking 15-LOX, DPA-metabolites, and the bioactivities is still unclear, and the free radicals generated in DPA peroxidation have never been characterized. In this study, we have studied radicals formed from both soybean and human cellular (PC3-15LOS cells) 15-LOX-catalyzed peroxidation of DPAs at different pH’s using a combination of LC/ESR/MS with the spin trapping technique. We observed a total of three carbon-centered radicals formed in 15-LOX/DPA (n-3) stemming from its 7-, 17- and 20-hydroperoxides, while only one formed from 17-hydroperoxide in DPA (n-6). A change in the reaction pH from 8.5 (15-LOX enzyme optimum) to 7.4 (physiological) and to 6.5 (tumor, acidic) not only decreased the total radical formation but also altered the preferred site of oxygenation. This pH-dependent alteration of radical formation and oxygenation pattern may have significant implications and provide a basis for our ongoing investigations of LOXs as well as fatty acids in cancer biology. PMID:21807091

  19. Validation of ESR analyzer using Westergren ESR method.

    PubMed

    Sikka, Meera; Tandon, Rajesh; Rusia, Usha; Madan, Nishi

    2007-07-01

    Erythrocyte sedimentation rate (ESR) is one of the most frequently ordered laboratory test. ESR analyzers were developed to provide a quick and efficient measure of ESR. We compared the results of ESR obtained by an ESR analyzer with those by the Westergren method in a group of 75 patients Linear regression analysis showed a good correlation between the two results (r = 0.818, p < 0.01). The intra class correlation was 0.82. The analyzer method had the advantages of safety, decreased technician time and improved patient care by providing quick results.

  20. EXAFS study of Cu/C catalysts

    NASA Astrophysics Data System (ADS)

    Kriventsov, V. V.; Klimov, O. V.; Kikhtyanin, O. V.; Ione, K. G.; Kochubey, D. I.

    2000-06-01

    A local arrangement of copper in Cu/C catalysts for dimethylcarbonate synthesis was studied by EXAFS. The samples with various Cu content were prepared by impregnating of carbon carrier "Sibunit" with the alcohol solution of CuCl 2. It was determined, that the oxygen atoms from surface groups of carrier always enter into copper surrounding and the relative content of oxygen drops with the increase of Cu content in the samples. The structure of surface copper compounds for initial catalysts was proposed. Thus, samples with low Cu content (9×10 -4 mol/g-cat) possess surface compounds [carrier-COO-CuCl] or [carrier-CO-CuCl], further, by increasing copper content a second surface layer consisting of hydrated CuCl 2 non-bounded with carrier is formed.

  1. Regulation of the Edwardsiella ictaluri Type III Secretion System by pH and Phosphate Concentration through EsrA, EsrB, and EsrC ▿

    PubMed Central

    Rogge, Matthew L.; Thune, Ronald L.

    2011-01-01

    A recently described Edwardsiella ictaluri type III secretion system (T3SS) with functional similarity to the Salmonella pathogenicity island 2 T3SS is required for replication in channel catfish head-kidney-derived macrophages (HKDM) and virulence in channel catfish. Quantitative PCR and Western blotting identified low pH and phosphate limitation as conducive to expression of the E. ictaluri T3SS, growth conditions that mimic the phagosomal environment. Mutagenesis studies demonstrated that expression is under the control of the EsrAB two-component regulatory system. EsrB also induces upregulation of the AraC-type regulatory protein EsrC, which enhances expression of the EscB/EseG chaperone/effector operon in concert with EsrB and induces expression of the pEI1-encoded effector, EseH. EsrC also induces expression of a putative type VI secretion system translocon protein, EvpC, which is secreted under the same low-pH conditions as the T3SS translocon proteins. The pEI2-encoded effector, EseI, was upregulated under low-pH and low-phosphate conditions but not in an EsrB- or EsrC-dependent manner. Mutations of EsrA and EsrB both resulted in loss of the ability to replicate in HKDM and full attenuation in the channel catfish host. Mutation of EsrC did not affect intracellular replication but did result in attenuation in catfish. Although EsrB is the primary transcriptional regulator for E. ictaluri genes within the T3SS pathogenicity island, EsrC regulates expression of the plasmid-carried effector eseH and appears to mediate coordinated expression of the T6SS with the T3SS. PMID:21551284

  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. Thermoluminescence, ESR and x-ray diffraction studies of CaSO4 : Dy phosphor subjected to post preparation high temperature thermal treatment

    NASA Astrophysics Data System (ADS)

    Bakshi, A. K.; Patwe, S. J.; Bhide, M. K.; Sanyal, B.; Natarajan, V.; Tyagi, A. K.; Kher, R. K.

    2008-01-01

    Thermoluminescence (TL), electron spin resonance (ESR) and x ray diffraction studies of CaSO4 : Dy phosphor subjected to post preparation high temperature treatment were carried out. Analysis of the TL glow curve indicated that the dosimetric glow peak at 240 °C reduces, whereas the low temperature satellite peak increases with the increase in the annealing temperature in the range 650-1000 °C. The influence of the annealing atmosphere on the TL glow curve structure was also observed. Reduction of the photoluminescence intensity of the annealed phosphor indicated that the environment of Dy3+ ions might have undergone some change due to high temperature treatment. Reduction in the ESR signal intensity corresponding to O_{3}^{-} and SO_{3}^{-} radicals was observed initially with the increase in the annealing temperaure; subsequently their intensity increased with temperature. Signals due to the SO_{4}^{-} radical vanished, when the phosphor was annealed beyond 800 °C. A signal corresponding to SH2- radicals was also observed in the ESR spectra for samples subjected to annealing in the temperature regime 800-1000 °C. XRD of the in situ annealed phosphor showed a change in the unit cell parameters. An endothermic peak at 860 °C in the DTA spectrum was observed.

  4. ESR study of order and dynamics in lecithin liposomes with high cholesterol content

    NASA Astrophysics Data System (ADS)

    Costanzo, R.; De Paoli, T.; Ihlo, J. E.; Hager, A. A.; Farach, H. A.; Poole, C. P.; Knight, J. M.

    1994-02-01

    Previous studies have shown that increasing amounts of cholesterol in phosphatidyl choline liposomes (involving cholesterol/lecithin ratios up to 1), produce an increase in order and a decrease in mobility of the phospholipids in the bilayer. The present work focuses on the order and dynamics of the phospholipids in soybean and egg yolk liposomes with cholesterol/lecithin (chol/lec) ratios as high as 2. The influence of cholesterol on the order parameter and correlation times of 5-, 12- and 16-doxyl stearic acid probes, is analyzed for both types of liposomes. The order parameter increases continuously with the increase of the amount of cholesterol although the correlation time at first increases, then it levels off at a chol/lec ratio of 1, and thereafter shows a small, gradual decrease up to a ratio of 2. A statistical model of cholesterol substitution on the lecithin lattice was employed to explain the correlation time results.

  5. ESR study of some gamma irradiated amino acids and condensed 1,4-dihydropyridines

    NASA Astrophysics Data System (ADS)

    Aydın, Murat; Şimşek, Rahime; Gündüz, Miyase Gözde; Şafak, Cihat; Osmanoğlu, Y. Emre

    2013-03-01

    L-alanine methyl ester hydrochloride, 2-aminoisobutyric acid and some condensed 1,4-dihydropyridine derivatives (Compounds R1-R4) were gamma irradiated, the induced free radicals was investigated at room temperature by electron spin resonance techniques. The observed paramagnetic species of amino acids compounds were attributed to the CH3ĊHCOOCH3 and (CH3)2ĊCOOH radicals, respectively. The observed spectra of the 1,4-dihydropyridine derivatives interpreted in terms of some type of amine radical fragments. The spectra were computer simulated and the g values of the radicals and the hyperfine structure constants of the unpaired electron with nearby protons and 14N nucleus were determined. In this study, the observed paramagnetic species were found to be stable at room temperature more than 2 months.

  6. Generation and characterization of alkali metal clusters in Y-FAU zeolites. An ESR and MAS NMR spectroscopic study

    NASA Astrophysics Data System (ADS)

    Hannus, István; Béres, Attila; Nagy, János B.; Halász, János; Kiricsi, Imre

    1997-06-01

    Charged and neutral metal clusters of various compositions and sizes can be prepared by controlling the alkali metal content by the decomposition of alkali azides and the composition of the host zeolite by ion-exchange. ESR signals show that electron transfer from alkali metal atoms to alkali metal cations does occur, but in a direction opposite to that predicted by the gas-phase thermochemistry. Alkali metal clusters proved to be very active basic catalytic centers.

  7. 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.

  8. 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.

  9. Study of the oxidation state of copper in La 1.8Sr .2CuO 4

    NASA Astrophysics Data System (ADS)

    Zhang, Y.-C.; Liu, J.-H.; Dwight, K.; Rieger, P. H.; Wold, A.

    1987-09-01

    Samples of La 1.8Sr .2CuO 4 were prepared by decomposition of the nitrates. From magnetic susceptibility, temperature programmed reduction and ESR measurements it is concluded that the Cu(II) has most probably disproportionated to Cu(I), Cu(III).

  10. Studies on Cu(II) ternary complexes involving an aminopenicillin drug and imidazole containing ligands

    NASA Astrophysics Data System (ADS)

    Regupathy, Sthanumoorthy; Nair, Madhavan Sivasankaran

    2010-02-01

    Equilibrium studies on the ternary complex systems involving ampicillin (amp) as ligand (A) and imidazole containing ligands viz., imidazole (Him), benzimidazole (Hbim), histamine (Hist) and histidine (His) as ligands (B) at 37 °C and I = 0.15 mol dm -3 (NaClO 4) show the presence of CuABH, CuAB and CuAB 2. The proton in the CuABH species is attached to ligand A. In the ternary complexes the ligand, amp(A) binds the metal ion via amino nitrogen and carbonyl oxygen atom. The CuAB (B = Hist/His)/CuAB 2 (B = Him/Hbim) species have also been isolated and the analytical data confirmed its formation. Non-electrolytic behavior and monomeric type of chelates have been assessed from their low conductance and magnetic susceptibility values. The electronic and vibrational spectral results were interpreted to find the mode of binding of ligands to metal and geometry of the complexes. This is also supported by the g tensor values calculated from ESR spectra. The thermal behaviour of complexes were studied by TGA/DTA. The redox behavior of the complexes has been studied by cyclic voltammetry. The antimicrobial activity and CT DNA cleavage study of the complexes show higher activity for ternary complexes.

  11. Continuous-wave far-infrared ESR spectrometer for high-pressure measurements.

    PubMed

    Náfrádi, Bálint; Gaál, Richárd; Sienkiewicz, Andrzej; Fehér, Titusz; Forró, László

    2008-12-01

    We present a newly-developed microwave probe for performing sensitive high-field/multi-frequency electron spin resonance (ESR) measurements under high hydrostatic pressures. The system consists of a BeCu-made pressure-resistant vessel, which accommodates the investigated sample and a diamond microwave coupling window. The probe's interior is completely filled with a pressure-transmitting fluid. The setup operates in reflection mode and can easily be assembled with a standard oversized microwave circuitry. The probe-head withstands hydrostatic pressures up to 1.6 GPa and interfaces with our home-built quasi-optical high-field ESR facility, operating in a millimeter/submillimeter frequency range of 105-420 GHz and in magnetic fields up to 16 T. The overall performance of the probe was tested, while studying the pressure-induced changes in the spin-relaxation mechanisms of a quasi-1D conducting polymer, KC(60). The preliminary measurements revealed that the probe yields similar signal-to-noise ratio to that of commercially available low-frequency ESR spectrometers. Moreover, by observing the conduction electron spin resonance (CESR) linewidth broadening for KC(60) in an unprecedented microwave frequency range of 210-420 GHz and in the pressure range of up to 1.6 GPa, we demonstrate that a combination of high-pressure ESR probe and high-field/multi-frequency spectrometer allows us to measure the spin relaxation rates in conducting spin systems, like the quasi-1D conductor, KC(60).

  12. Metal-insulator transition in RbC60 polymer fulleride studied by ESR and electron-spin relaxation

    NASA Astrophysics Data System (ADS)

    Atsarkin, V. A.; Demidov, V. V.; Vasneva, G. A.

    1997-10-01

    The ESR intensity, line shape, and longitudinal electron-spin relaxation in the polymer phase of the RbC60 fulleride are investigated in the temperature range 4.2ESR line can be separated into two Lorentzian components ascribed to conduction electrons and some localized paramagnetic centers (with concentration of about 0.03 per formula unit) with allowance made for the relaxation bottleneck. The decrease of the conduction-electron susceptibility obeys an activation law with the characteristic energy Δ/kB=80+/-10 K related to the opening of a gap 2Δ~100 cm -1. The same quantity is found by analyzing both longitudinal and transverse relaxation caused by fluctuations of internal fields with correlation time τc~ exp(2Δ/kBT). Below 25 K, the temperature dependencies of the linewidth and the relaxation times change abruptly, revealing the development of a new ordered state. The nature of this state is discussed.

  13. 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.

  14. 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.

  15. 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.

  16. A two-dimensional Fourier transform electron-spin resonance (ESR) study of nuclear modulation and spin relaxation in irradiated malonic acid

    NASA Astrophysics Data System (ADS)

    Lee, Sanghyuk; Patyal, Baldev R.; Freed, Jack H.

    1993-03-01

    Nuclear modulation in electron-spin-echo spectroscopy is conventionally studied by one-dimensional electron-spin-echo envelope modulation (1D-ESEEM). Two-dimensional Fourier transform electron-spin resonance (2D-FTESR) studies of nuclear modulation have the promise of enhancing the spectral resolution and clarifying the key details of the relaxation processes. We present a 2D-FTESR study on single proton nuclear modulation from γ-irradiated malonic acid single crystals to test the validity of the Gamliel-Freed theory and to assess the value of the new methods. The two pulse spin-echo correlation spectroscopy (SECSY) spectra as a function of orientation of the single crystal show very good agreement with the Gamliel-Freed theory extended to the general case of nonaxially symmetric hyperfine interaction. It is very simply affected by spin relaxation, such that relative intensities are essentially unaffected. Thus SECSY-ESR can most reliably be utilized for studying nuclear modulation. Stimulated SECSY provides the simplest nuclear modulation patterns, which, however, do exhibit the suppression effect well known in three-pulse ESEEM studies. Two-dimensional electron-electron double resonance (2D-ELDOR) provides nuclear modulation patterns similar to that of SECSY-ESR, so the suppression effect is absent. Both three-pulse methods exhibit complex relaxation behavior which can affect relative intensities. This is a feature characteristic of three-pulse ESEEM, but is not well understood. It is shown how the 2D-FTESR methods enable one to obtain the details of the complex spin relaxation, and in the process, obtain very good agreement between experiment and theory. 2D-ELDOR exhibits exchange cross peaks as well as coherence peaks from the nuclear modulation. It is shown how experiments, as a function of mixing time, enable one to separate the effects of the two. It is pointed out that such experiments are in the spirit of 3D spectroscopy. A new observation of the

  17. In vivo dosimetry in the urethra using alanine/ESR during (192)Ir HDR brachytherapy of prostate cancer--a phantom study.

    PubMed

    Anton, Mathias; Wagner, Daniela; Selbach, Hans-Joachim; Hackel, Thomas; Hermann, Robert Michael; Hess, Clemens Friedrich; Vorwerk, Hilke

    2009-05-07

    A phantom study for dosimetry in the urethra using alanine/ESR during (192)Ir HDR brachytherapy of prostate cancer is presented. The measurement method of the secondary standard of the Physikalisch-Technische Bundesanstalt had to be slightly modified in order to be able to measure inside a Foley catheter. The absorbed dose to water response of the alanine dosimetry system to (192)Ir was determined with a reproducibility of 1.8% relative to (60)Co. The resulting uncertainty for measurements inside the urethra was estimated to be 3.6%, excluding the uncertainty of the dose rate constant Lambda. The applied dose calculated by a treatment planning system is compared to the measured dose for a small series of (192)Ir HDR irradiations in a gel phantom. The differences between the measured and applied dose are well within the limits of uncertainty. Therefore, the method is considered to be suitable for measurements in vivo.

  18. In vivo dosimetry in the urethra using alanine/ESR during 192Ir HDR brachytherapy of prostate cancer—a phantom study

    NASA Astrophysics Data System (ADS)

    Anton, Mathias; Wagner, Daniela; Selbach, Hans-Joachim; Hackel, Thomas; Hermann, Robert Michael; Hess, Clemens Friedrich; Vorwerk, Hilke

    2009-05-01

    A phantom study for dosimetry in the urethra using alanine/ESR during 192Ir HDR brachytherapy of prostate cancer is presented. The measurement method of the secondary standard of the Physikalisch-Technische Bundesanstalt had to be slightly modified in order to be able to measure inside a Foley catheter. The absorbed dose to water response of the alanine dosimetry system to 192Ir was determined with a reproducibility of 1.8% relative to 60Co. The resulting uncertainty for measurements inside the urethra was estimated to be 3.6%, excluding the uncertainty of the dose rate constant Λ. The applied dose calculated by a treatment planning system is compared to the measured dose for a small series of 192Ir HDR irradiations in a gel phantom. The differences between the measured and applied dose are well within the limits of uncertainty. Therefore, the method is considered to be suitable for measurements in vivo.

  19. Isotope effects in ESR spectroscopy.

    PubMed

    Stößer, Reinhard; Herrmann, Werner

    2013-06-07

    In order to present the relationship between ESR spectroscopy and isotope effects three levels are considered: (i) ESR spectroscopy is described on a general level up to the models for interpretation of the experimental spectra, which go beyond the usually used time and mass independent spin-Hamilton operator, (ii) the main characteristics of the generalized isotope effects are worked out, and finally (iii) the basic, mainly quantum mechanical effects are used to describe the coupling of electron spins with the degrees of freedom, which are accessible under the selected conditions, of the respective paramagnetic object under investigation. The ESR parameters and the respective models are formalized so far, that they include the time and mass depending influences and reflect the specific isotope effects. Relations will be established between the effects in ESR spectra to spin relaxation, to spin exchange, to the magnetic isotope effect, to the Jahn-Teller effects, as well as to the influence of zero-point vibrations. Examples will be presented which demonstrate the influence of isotopes as well as the kind of accessible information. It will be differentiated with respect to isotope effects in paramagnetic centres itself and in the respective matrices up to the technique of ESR imaging. It is shown that the use of isotope effects is indispensable in ESR spectroscopy.

  20. Theoretical studies of CO and NO on CuO and Cu 2O(110) surfaces

    NASA Astrophysics Data System (ADS)

    Duan, Yuhua; Zhang, Kaiming; Xie, Xide

    1994-12-01

    The characteristics of CO and NO adsorption on surfaces of CuO(110) and Cu 2O(110) have been studied by using the self-consistent-charge discrete variational X a method (SCC-DV-X a). The calculated results show that the CO and NO molecules are perpendicularly adsorbed on cuprous ions of Cu 2O and cupric ions of CuO, respectively and with oxygen pointing upward in both cases. The order of chemisorption energy of the four adsorbed systems is: CuO-NO > Cu 2O-CO > Cu 2O-NO > CuO-CO. In all chemisorptions discussed d orbitals of Cu do play an important role.

  1. Electronic and optical properties of Cu, CuO and Cu2O studied by electron spectroscopy

    NASA Astrophysics Data System (ADS)

    Tahir, Dahlang; Tougaard, Sven

    2012-05-01

    The electronic and optical properties of Cu, CuO and Cu2O were studied by x-ray photoelectron spectroscopy (XPS) and reflection electron energy-loss spectroscopy (REELS). We report detailed Cu 2p, Cu LVV, O 1s and O KLL spectra which are in good agreement with previous results. REELS spectra, recorded for primary energies in the range from 150 to 2000 eV, were corrected for multiple inelastically scattered electrons to determine the effective inelastic scattering cross section. The dielectric functions and optical properties were determined by comparing the experimental inelastic electron scattering cross section with a simulated cross section calculated within the semi-classical dielectric response model in which the only input is Im(-1/ɛ) by using the QUEELS-ɛ(k,ω)-REELS software package. By Kramers-Kronig transformation of the determined Im(-1/ɛ), the real and imaginary parts (ɛ1 and ɛ2) of the dielectric function, and the refractive index n and extinction coefficient k were determined for Cu, CuO, and Cu2O in the 0-100 eV energy range. Observed differences between Cu, CuO and Cu2O are mainly due to modifications of the 3d and O 2p electron configurations.

  2. Development of Prototype Production ESR Facilities

    DTIC Science & Technology

    1977-07-01

    4 3^ SCHEMATIC OF A STEEL FUNNEL MOLD ESR INGOT CASTING SET-UP 6 4. SCHEMATIC OF ESR HOLLOW INGOT MANUFACTURING SYSTEM 8 5. ESR HOLLOW INGOT...UP SLAG SKIN ESR INGOT IN GOT STOOL FIGURE 3. SCHEMATIC OTA STEEL FUNNEL MOLD (MOVES UPjESR INGOT CASTING SET UP Title: Development of...Prototype Production ESR Facilities Because the steel mold was heavy, a two-sided support and lift system was used. An x-ray molten metal scanning device

  3. Physics book: CRYRING@ESR

    NASA Astrophysics Data System (ADS)

    Lestinsky, M.; Andrianov, V.; Aurand, B.; Bagnoud, V.; Bernhardt, D.; Beyer, H.; Bishop, S.; Blaum, K.; Bleile, A.; Borovik, At.; Bosch, F.; Bostock, C. J.; Brandau, C.; Bräuning-Demian, A.; Bray, I.; Davinson, T.; Ebinger, B.; Echler, A.; Egelhof, P.; Ehresmann, A.; Engström, M.; Enss, C.; Ferreira, N.; Fischer, D.; Fleischmann, A.; Förster, E.; Fritzsche, S.; Geithner, R.; Geyer, S.; Glorius, J.; Göbel, K.; Gorda, O.; Goullon, J.; Grabitz, P.; Grisenti, R.; Gumberidze, A.; Hagmann, S.; Heil, M.; Heinz, A.; Herfurth, F.; Heß, R.; Hillenbrand, P.-M.; Hubele, R.; Indelicato, P.; Källberg, A.; Kester, O.; Kiselev, O.; Knie, A.; Kozhuharov, C.; Kraft-Bermuth, S.; Kühl, T.; Lane, G.; Litvinov, Yu. A.; Liesen, D.; Ma, X. W.; Märtin, R.; Moshammer, R.; Müller, A.; Namba, S.; Neumeyer, P.; Nilsson, T.; Nörtershäuser, W.; Paulus, G.; Petridis, N.; Reed, M.; Reifarth, R.; Reiß, P.; Rothhardt, J.; Sanchez, R.; Sanjari, M. S.; Schippers, S.; Schmidt, H. T.; Schneider, D.; Scholz, P.; Schuch, R.; Schulz, M.; Shabaev, V.; Simonsson, A.; Sjöholm, J.; Skeppstedt, Ö.; Sonnabend, K.; Spillmann, U.; Stiebing, K.; Steck, M.; Stöhlker, T.; Surzhykov, A.; Torilov, S.; Träbert, E.; Trassinelli, M.; Trotsenko, S.; Tu, X. L.; Uschmann, I.; Walker, P. M.; Weber, G.; Winters, D. F. A.; Woods, P. J.; Zhao, H. Y.; Zhang, Y. H.

    2016-09-01

    The exploration of the unique properties of stored and cooled beams of highly-charged ions as provided by heavy-ion storage rings has opened novel and fascinating research opportunities in the realm of atomic and nuclear physics research. Since the late 1980s, pioneering work has been performed at the CRYRING at Stockholm (Abrahamsson et al. 1993) and at the Test Storage Ring (TSR) at Heidelberg (Baumann et al. 1988). For the heaviest ions in the highest charge-states, a real quantum jump was achieved in the early 1990s by the commissioning of the Experimental Storage Ring (ESR) at GSI Helmholtzzentrum für Schwerionenforschung (GSI) in Darmstadt (Franzke 1987) where challenging experiments on the electron dynamics in the strong field regime as well as nuclear physics studies on exotic nuclei and at the borderline to atomic physics were performed. Meanwhile also at Lanzhou a heavy-ion storage ring has been taken in operation, exploiting the unique research opportunities in particular for medium-heavy ions and exotic nuclei (Xia et al. 2002).

  4. Irradiation detection of coffee mate by electron spin resonance (ESR)

    NASA Astrophysics Data System (ADS)

    Özsayin, Fulya; Polat, Mustafa

    2011-06-01

    Un-irradiated coffee mate samples do not exhibit any ESR signal. However, the samples exposed to UV and gamma radiation exhibit an ESR singlet and a large unresolved ESR signal, respectively. The dose-response curves of the samples exposed to UV and gamma radiations were found to be described well by an exponential and linear functions, respectively. Variable temperature and fading studies at room temperature showed that the radiation-induced radicals in coffee mate sample are very sensitive to temperature. The discrimination between un-irradiated and irradiated coffee mate samples can be done just comparing their ESR spectra. However, determination of the radiation dose received by the sample cannot be possible because of the fast decay of signal intensity at room temperature.

  5. 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

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

    PubMed

    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 [H(2)O(2)] 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.

  7. 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.

  8. Magnetic phase transition of high-pressure phase (VO)2P2O7 studied by high-field ESR measurements

    NASA Astrophysics Data System (ADS)

    Hiraka, K.; Nagasaka, Y.; Kunimoto, T.; Inagaki, Y.; Okubo, S.; Ohta, H.; Saito, T.; Azuma, M.; Takano, M.

    2004-05-01

    The high-pressure phase of (VO)2P2O7 (HP-VOPO) is a S=1/2 Heisenberg antiferromagnetic alternating chain compound with one spin gap. The high-field ESR measurements of the HP-VOPO single crystal have been performed using the pulsed magnetic field up to 30T. Small anomaly is observed in ESR mode for both a- and b-axis. The linewidth became broad around Bc=20T when the field is applied along the a- and b-axis. The magnetic state of HP-VOPO above Bc will be discussed.

  9. 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

  10. Theoretical study of the electron affinities of Cu, Cu2, and Cu3

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1988-01-01

    The modified pair functional method is used here to compute the electron affinities of the negative ions of Cu, Cu2, and Cu3 to equal relative accuracy. The results show that, while the extra electron in Cu2(-) occupies a sigma(u) antibonding orbital, the orbital is polarized to reduce the density in the internuclear rergion. The calculations also show that Cu3(-) is a closed-shell linear molecule in its ground state, and that there is an excited triplet state about 0.7 eV higher in energy. This strongly suggests that photodetachment from the excited triplet state is responsible for the low energy structure observed in the photoelectron spectrum of Cu3(-).

  11. The influence of ESR1 rs9340799 and ESR2 rs1256049 polymorphisms on prostate cancer risk.

    PubMed

    Fu, Chenying; Dong, Wen-Qi; Wang, Ani; Qiu, Guozhen

    2014-08-01

    Estrogen receptor 1 (ESR1) and estrogen receptor 2 (ESR2) may play a role in the development of prostate cancer. Many studies focused on ESR1 rs9340799 and ESR2 rs1256049 polymorphisms to explore associations with prostate cancer risk. These studies showed inconsistent and conflicting results. The aim of this meta-analysis was to investigate the pooled association of ESR1 rs9340799 and ESR2 rs1256049 polymorphisms with prostate cancer risk. A systematic literature search was conducted to identify related studies (up to February 2014) in several online databases including PubMed, Google Scholar, CNKI and Wanfang online libraries. A total of 16 eligible articles were enrolled in this updated meta-analysis. The result suggested that ESR1 rs9340799 polymorphism was significantly associated with prostate cancer in overall populations (GG+GA vs. AA: P = 0.002; G vs. A: P = 0.004), Caucasians (GG+GA vs. AA: P = 0.008; G vs. A: P = 0.016) and Africans (GG+GA vs. AA: P = 0.005; G vs. A: P = 0.006), but not in Asians (GG+GA vs. AA: P = 0.462; G vs. A: P = 0.665). The result also showed that there was a significant association between ESR2 rs1256049 polymorphism and prostate cancer in Caucasians (AA+AG vs. GG: P = 0.016; A vs. G: P = 0.005), but no association in overall populations (AA+AG vs. GG: P = 0.826; A vs. G: P = 0.478), Asians (AA+AG vs. GG: P = 0.177; A vs. G: P = 0.703) and Africans (AA+AG vs. GG: P = 0.847; A vs. G: P = 0.707). The cumulative meta-analysis and sensitivity analysis showed the results were robust. In conclusion, this meta-analysis indicated that ESR1 rs9340799 polymorphism was associated with prostate cancer risk in overall populations, Caucasians and Africans, while ESR2 rs1256049 polymorphism was associated with prostate cancer risk in Caucasians. However, the biological mechanisms need to be further investigated.

  12. 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.

  13. 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.

  14. Synthesis, structural characterization, thermal and electrochemical studies of mixed ligand Cu(II) complexes containing 2-phenyl-3-(benzylamino)-1,2-dihydroquinazoline-4-(3H)-one and bidentate N-donor ligands.

    PubMed

    Sawant, V A; Yamgar, B A; Sawant, S K; Chavan, S S

    2009-12-01

    Some mixed ligand Cu(II) complexes of the type [Cu(L)(en)X(2)] (1a-3a), [Cu(L)(en)](ClO(4))(2) (4a), [Cu(L)(phen)X(2)] (1b-3b) and [Cu(L)(phen)](ClO(4))(2) (4b) [where L = 2-phenyl-3-(benzylamino)-1,2-dihydroquinazoline-4-(3H)-one; en = ethylenediamine; phen = 1,10-phenanthroline; X = Cl(-), N(3)(-) and NCS(-)] have been prepared. The complexes were characterized on the basis of elemental analysis, molar conductance, magnetic moment, IR, UV-vis, mass, ESR and thermal studies. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for 1a-3a and 1b-3b and square-planer geometry for 4a and 4b. The ESR spectral data of complexes provided information about their structure on the basis of Hamiltonian parameters and degree of covalency. The electrochemical behaviour of mixed ligand Cu(II) complexes was studied which showed that complexes of phen appear at more positive potential as compared to those for corresponding en complexes.

  15. Dzyaloshinsky-Moriya Interaction and the Ground State in S = 3/2 Perfect Kagome Lattice Antiferromagnet KCr3(OH)6(SO4)2 (Cr-Jarosite) Studied by X-Band and High-Frequency ESR

    NASA Astrophysics Data System (ADS)

    Okubo, Susumu; Nakata, Ryohei; Ikeda, Shohei; Takahashi, Naoki; Sakurai, Takahiro; Zhang, Wei-Min; Ohta, Hitoshi; Shimokawa, Tokuro; Sakai, Tôru; Okuta, Koji; Hara, Shigeo; Sato, Hirohiko

    2017-02-01

    A single-crystal S = 3/2 perfect kagome lattice antiferromagnet, KCr3(OH)6(SO4)2 (Cr-jarosite), has been studied by X-band and high-frequency electron spin resonance (ESR). The g-values perpendicular to the kagome plane (c-axis) and in the plane were determined to be gc = 1.9704 ± 0.0002 and gξ = 1.9720 ± 0.0003, respectively, by high-frequency ESR observed at 265 K. Antiferromagnetic resonances (AFMRs) with an antiferromagnetic gap of 120 GHz were observed at 1.9 K, which is below TN = 4.5 K. The analysis of AFMR modes using the conventional molecular field theory gave dp = 0.27 K and dz = 0.07 K, where dp and dz are in-plane and out-of-plane components of d vector of the Dzyaloshinsky-Moriya (DM) interaction, respectively. On the basis of these results and the exchange interaction of J = 6.15 K estimated by Okuta et al., the ground state of Cr-jarosite was discussed in connection with the Monte Carlo simulation results with classical Heisenberg spins on the kagome lattice by Elhajal et al. Finally, the angular dependence of the linewidth and lineshape observed at 296 K by X-band ESR showed the typical behavior of a two-dimensional Heisenberg antiferromagnet, suggesting the good two-dimensionality of Cr-jarosite.

  16. Slow molecular motion of different spin probes in a model glycerol—water matrix studied by double modulation ESR

    NASA Astrophysics Data System (ADS)

    Valić, S.; Rakvin, B.; Veksli, Z.; Pečar, S.

    1992-11-01

    The slow molecular motion of several deuterated and undeuterated spin probes differing in size and shape, embedded in a model glycerol—water matrix, have been studied by double-modulated electron spin resonance (DMESR). The DMESR spectra as a function of temperature reveal two motional regions. From the experimental linewidths of both deuterated and undeuterated spin probes in the lower temperature region and simulated data based on the variation of T1 relaxation, two different dynamics of the -CH 3 groups attached to piperidine ring were resolved. Our results indicate that the onset of the whole spin probe motion depends on the type of probe and the matrix density.

  17. Metal-independent production of hydroxyl radicals by halogenated quinones and hydrogen peroxide: an ESR spin trapping study.

    PubMed

    Zhu, Ben-Zhan; Zhao, Hong-Tao; Kalyanaraman, Balaraman; Frei, Balz

    2002-03-01

    The metal-independent production of hydroxyl radicals (*OH) from H(2)O(2) and tetrachloro-1,4-benzoquinone (TCBQ), a carcinogenic metabolite of the widely used wood-preservative pentachlorophenol, was studied by electron spin resonance methods. When incubated with the spin trapping agent 5,5-dimethyl-1-pyrroline N-oxide (DMPO), TCBQ and H(2)O(2) produced the DMPO/*OH adduct. The formation of DMPO/*OH was markedly inhibited by the *OH scavenging agents dimethyl sulfoxide (DMSO), ethanol, formate, and azide, with the concomitant formation of the characteristic DMPO spin trapping adducts with *CH(3), *CH(CH(3))OH, *COO(-), and *N(3), respectively. The formation of DMPO/*OH and DMPO/*CH(3) from TCBQ and H(2)O(2) in the absence and presence, respectively, of DMSO was inhibited by the trihydroxamate compound desferrioxamine, accompanied by the formation of the desferrioxamine-nitroxide radical. In contrast, DMPO/*OH and DMPO/*CH(3) formation from TCBQ and H(2)O(2) was not affected by the nonhydroxamate iron chelators bathophenanthroline disulfonate, ferrozine, and ferene, as well as the copper-specific chelator bathocuproine disulfonate. A comparative study with ferrous iron and H(2)O(2), the classic Fenton system, strongly supports our conclusion that *OH is produced by TCBQ and H(2)O(2) through a metal-independent mechanism. Metal-independent production of *OH from H(2)O(2) was also observed with several other halogenated quinones.

  18. Ordered and Disordered Phases Coexist in Plasma Membrane Vesicles of RBL-2H3 Mast Cells. An ESR Study

    PubMed Central

    Ge, Mingtao; Gidwani, Arun; Brown, H. Alex; Holowka, David; Baird, Barbara; Freed, Jack H.

    2003-01-01

    Four chain spin labels and a spin-labeled cholestane were used to study the dynamic structure of plasma membrane vesicles (PMV) prepared from RBL-2H3 mast cells at temperatures ranging from 22°C to 45°C. Analysis shows that the spectra from most labels consist of two components. The abundant spectral components exhibit substantial ordering that is intermediate between that of a liquid-ordered (Lo) phase, and that of a liquid-crystalline (Lc) phase as represented by model membranes. Also, rotational diffusion rates of the spin labels are comparable to those in the Lo phase. In contrast, the ordering for the less abundant components is much lower. These results indicate that a Lo-like region or phase (the abundant component) and an Lc-like region or phase (the less abundant component) coexist in the PMV. In contrast, membranes reconstituted from extracted lipids exhibit the more ordered phase only. This suggests that membrane-associated proteins are important for the coexistence of Lo-like and Lc-like regions in the plasma membrane. In addition, binding of the myristoylated protein, ARF6 to PMV, leads to a new spectral component for a headgroup lipid spin label that indicates the formation of plasma membrane defects by this low molecular weight GTPase. PMID:12885671

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

    PubMed

    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 (HL(1)), 2-((4-oxo-4H-chromen-3-yl)methylneamino) benzoicacid (HL(2)), 3-((3-hydroxypyridin-2-ylimino)methyl)-4H-chromen-4-one (HL(3)) and 3-((2-mercaptophenylimino)methyl)-4H-chromen-4-one (HL(4)). 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.

  20. Photolysis of NaClO3 and KClO3 at 26 K studied by optical and ESR spectroscopy

    NASA Astrophysics Data System (ADS)

    Bjerre, Nis

    1982-03-01

    Two types of defects are formed when crystalline NaClO3 and KClO3 are photolyzed at 26 K with monochromatic light of a wavelength corresponding to the fundamental absorption. One type of defects absorbs around 380 nm and has an ESR spectrum characteristic of trapped O2. The other type of defects absorbs around 270 and 580 nm and has no ESR spectrum. The two types of defects are interconverted reversibly by bleaching within the respective absorption bands. Chemical analysis and isotopic labeling indicates that the defects consist of fragments of a single chlorate ion. The 380 nm absorption is assigned to charge transfer in the complex [ClO-,O2]; the 270 and 580 nm absorptions are assigned to [Cl-,O3]. Both the optical spectra and the mechanism of photolysis are represented by a model based on the enthalpies of formation of various configurations of one chlorine and three oxygen atoms.

  1. ESR

    MedlinePlus

    ... Muscle symptoms Other vague symptoms that cannot be explained This test may also be used to monitor ... failure Hyperviscosity Hypofibrinogenemia (decreased fibrinogen levels) Leukemia Low plasma protein (due to liver or kidney disease) Polycythemia ...

  2. On Cu(II) Cu(II) distance measurements using pulsed electron electron double resonance

    NASA Astrophysics Data System (ADS)

    Yang, Zhongyu; Becker, James; Saxena, Sunil

    2007-10-01

    The effects of orientational selectivity on the 4-pulse electron electron double resonance (PELDOR) ESR spectra of coupled Cu(II)-Cu(II) spins are presented. The data were collected at four magnetic fields on a poly-proline peptide containing two Cu(II) centers. The Cu(II)-PELDOR spectra of this peptide do not change appreciably with magnetic field at X-band. The data were analyzed by adapting the theory of Maryasov, Tsvetkov, and Raap [A.G. Maryasov, Y.D. Tsvetkov, J. Raap, Weakly coupled radical pairs in solids:ELDOR in ESE structure studies, Appl. Magn. Reson. 14 (1998) 101-113]. Simulations indicate that orientational effects are important for Cu(II)-PELDOR. Based on simulations, the field-independence of the PELDOR data for this peptide is likely due to two effects. First, for this peptide, the Cu(II) g-tensor(s) are in a very specific orientation with respect to the interspin vector. Second, the flexibility of the peptide washes out the orientation effects. These effects reduce the suitability of the poly-proline based peptide as a good model system to experimentally probe orientational effects in such experiments. An average Cu(II)-Cu(II) distance of 2.1-2.2 nm was determined, which is consistent with earlier double quantum coherence ESR results.

  3. 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.

  4. First principles study of properties of the oxidized Cu(100) and Cu(110)

    NASA Astrophysics Data System (ADS)

    Olenga, Antoine

    Copper based catalysts are of importance to a number of industrial processes including the synthesis of methanol, the reduction and decomposition of nitrogen oxides, and treatment of waste water. In copper catalysis surface oxidation and oxidic overlayers are believed to play a crucial role. In this work using density functional theory (DFT) within the generalized gradient approximation (GGA) we have studied the stability and associated electronic properties of the oxidized Cu(100) and Cu(110) surfaces. Especially, we have focused on studies of changes in the interlayer spacing, electron work function, binding energy, and density of states with oxygen coverage. We have examined the cases of various oxygen coverages of the non-reconstructed, missing row reconstructed Cu(100), and added row reconstructed Cu (110) surfaces. The first-principles calculations in this work have been performed using DMOl3 code. The obtained theoretical results have been compared with available experimental data.

  5. Conventional machining of ESR 4340 steel

    NASA Astrophysics Data System (ADS)

    Niji, K. K.

    1980-07-01

    This program involved the study of conventional machining of heat treated ESR 4340 steel (Rc 54-57). Initial effort involved a survey of available data regarding the machining of high strength steels with hardnesses of Rc 50 and above. A machining program was conducted, determining optimum tools and conditions for turning, drilling, face milling, end milling, and grinding operations. Effects of various parameters includng cutting speeds, feeds, depths of cut, and cutting fluids on tool life was determined. All the operations were found to be extremely difficult and applicaton of conventional procedures is not feasible. Tool lives remained short despite reductions in speeds and feeds. Conventional grinding methods induced detrimental residual tensile stresses along the surface, resulting in cracking, lapping, and untempered martensitic structures. Low stress grinding techniques were found to be applicable to this material when proper dressing procedures and reduced rates were used.

  6. ESR and iron status in pregnancy.

    PubMed

    Madan, N; Kapoor, S; Rusia, U; Sharma, S; Nayyar, V L; Sundaram, K R; Sood, S K

    1997-10-01

    ESR (Westergen) correlated significantly with the iron status (as measured by Hb concentration, haematocrit, red cell count, MCH, P/H ratio, serum iron, TIBC and percent saturation of transferrin) in a group of pregnant women (PW) at term. Serum ferritin correlated negatively with the ESR but the correlation was not statistically significant. Serum ferritin levels of < 50 micrograms/L were present in 9 (34.6%) PW with ESR > or = 50 mm 1st hour and 5 (19.2%) PW with ESR < 50 mm 1st hour. The mean ESR in PW was 55.7 (+/- 22.9) and was > or = 50 mm 1st hour in 50% and < 75 mm 1st hour in 82.7%. The difference in the mean ESR in anaemic and nonanaemic PW was highly significant (p < 0.001), 87.5% anaemic PW with serum ferritin > 50 micrograms/L had ESR > or = 50 mm 1st hour, suggesting the possible effect of chronic infection in raising ferritin levels in these PW.

  7. [Study of the effect of the microenvironment on magnetic resonance parameters of spin-labeled human serum albumin in a 2-mm ESR range].

    PubMed

    Krinichnyĭ, V I; Grinberg, O Ia; Likhtenshteĭn, G I; Lebedev, Ia S

    1985-01-01

    Basic values of g-tensor and Azz component of HF tensor of two spin labels and spin probe on HSA and nitroxyl radicals HO-15, HO-34 in the solvents of different polarity were measured by 2 mm band ESR of 2 mm range. Magnetic-resonance parameters of liophylized and water-solved spin-labeled HSA were shown to correspond to the parameters of the solvents of the label HO-15 and HO-34 in ethyl alcohol and water. A conclusion was drawn concerning the identity of microenvironment of the nitroxyl fragment of liophylized HSA and frozen solution of the label HO-15 and HO-34 in ethyl alcohol and solvatation of the nitroxyl fragment of spin-labeled HSA and label HO-15 (HO-34) by water molecules.

  8. ESR1 and its antagonist fulvestrant in pituitary adenomas.

    PubMed

    Gao, Hua; Xue, Yake; Cao, Lei; Liu, Qian; Liu, Chunhui; Shan, Xiaosong; Wang, Hongyun; Gu, Yi; Zhang, Yazhuo

    2017-03-05

    Estrogen has a key role in the pathogenesis of pituitary adenomas (PAs). The study was to evaluate the estrogen receptor alpha (ESR1) level in 289 PAs cases, its association with clinicopathologic features and serving as a target of cancer treatment. In this study, the ESR1 level was evaluated by tissue microarray (TMA). The effect of fulvestrant was determined by an animal model of prolactinoma established by subcutaneous injection of 17β-estradiol in F344 rats. The volume and weight of the pituitary were assessed in the different groups. The effects of fulvestrant on cell proliferation and cell invasion were explored in the pituitary adenoma cell lines GH3 and JT1-1. The ESR1-positive cells rates of 191/289 cases were more than 50%. And ESR1 high level cases (age≥50) were 103/133, and 88/156 in cases (age<50) (X(2) = 14.17, p = 0.0001). The average weight of the pituitary gland in F344 rat tumor model induced by 17-β-estradiol was 38.6 ± 11.2 mg, almost 6 times higher than control group (6.2 ± 1.7 mg). Fulvestrant significantly reduced the weight of the pituitary and its inhibition rate was 68.4 ± 8.3%. TUNEL assay and Western blotting showed that fulvestrant induced apoptotic cell death in vivo and in vitro. PTEN/MAPK signaling pathways were activated in response to fulvestrant treatment in GH3 cells. U0126 partly rescued cell viability of GH3 cells after fulvestrant exposure. ESR1 can be a potential target for PAs, especially for elder GHomas and NFPAs. Fulvestrant may be a new choice for the treatment of PAs.

  9. 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.

  10. Targeting ESR1-Mutant Breast Cancer

    DTIC Science & Technology

    2015-09-01

    Award Number: W81XWH-14-1-0360 TITLE: Targeting ESR1- Mutant Breast Cancer PRINCIPAL INVESTIGATOR: Geoffrey L. Greene, Ph.D. CONTRACTING...ADDRESS. 1. REPORT DATE September 2015 2. REPORT TYPE Annual 3. DATES COVERED 1 Sep 2014 - 31 Aug 2015 4. TITLE AND SUBTITLE Targeting ESR1- Mutant ...approved hormonal therapies and that more potent, selective estrogen receptor degraders (SERDs) will enable complete inhibition of mutant ER signaling and

  11. Targeting ESR1-Mutant Breast Cancer

    DTIC Science & Technology

    2015-09-01

    AWARD NUMBER: W81XWH-14-1-0359 TITLE: Targeting ESR1- Mutant Breast Cancer PRINCIPAL INVESTIGATOR: Dr. Sarat Chandarlapaty CONTRACTING...31 Aug 2015 4. TITLE AND SUBTITLE Targeting ESR1- Mutant Breast Cancer 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-14-1-0359 5c. PROGRAM ELEMENT...current FDA approved hormonal therapies and that more potent, selective estrogen receptor degraders (SERDs) will enable complete inhibition of mutant

  12. 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.

  13. Synthesis, spectral characterization and thermal studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with 2-amino benzoic acid- and 2-hydroxy benzoic acid thiophen-2-ylmethylene hydrazide

    NASA Astrophysics Data System (ADS)

    Singh, Vinod P.; Singh, Pooja

    2013-03-01

    A series of metal complexes of Co(II), Ni(II), Cu(II) and Zn(II) with 2-amino benzoic acid thiophen-2-ylmethylene hydrazide (Habth) and 2-hydroxy benzoic acid thiophen-2-ylmethylene hydrazide (Hhbth) have been synthesized. The complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, electronic, IR, NMR, ESR spectra and thermal studies (TGA and DTA). Molecular structure of the Habth ligand was determined by single crystal X-ray diffraction technique. Habth acts as a monobasic bidentate ligand in all its complexes bonding through a deprotonated Csbnd O- and lbond2 Cdbnd Nsbnd groups whereas, Hhbth acts as a monobasic bidentate in its Co(II) and Ni(II) complexes, bonding through a deprotonated Csbnd O- and lbond2 Cdbnd Nsbnd groups and as monobasic tridentate in Cu(II) and Zn(II) complexes bonding through lbond2 Cdbnd O, lbond2 Cdbnd Nsbnd and deprotonated (Csbnd O)- groups with the metal ion. Electronic spectra suggest a square planar geometry for Co(II), Ni(II) and Cu(II) complexes of Habth and Co(II) and Ni(II) complexes of Hhbth. However, the Cu(II) and Zn(II) complexes of Hhbth have octahedral geometry. The ESR spectra of Cu(II) complex of Hhbth in the solid state and in DMSO frozen solution show axial signals and suggest the presence of unpaired electron in d orbital of Cu(II). The Cu(II) complex of Habth in solid state shows isotropic signal, whereas, axial signal in DMSO frozen solution in the range of tetragonally distorted octahedral geometry due to interactions of DMSO molecules at axial positions. Thermal studies of some of the metal complexes show a multi-step decomposition pattern of bonded ligands in the complex.

  14. Microsatellites in the estrogen receptor (ESR1, ESR2) and androgen receptor (AR) genes and breast cancer risk in African American and Nigerian women.

    PubMed

    Zheng, Yonglan; Huo, Dezheng; Zhang, Jing; Yoshimatsu, Toshio F; Niu, Qun; Olopade, Olufunmilayo I

    2012-01-01

    Genetic variants in hormone receptor genes may be crucial predisposing factors for breast cancer, and microsatellites in the estrogen receptor (ESR1, ESR2) and androgen receptor (AR) genes have been suggested to play a role. We studied 258 African-American (AA) women with breast cancer and 259 hospital-based controls, as well as 349 Nigerian (NG) female breast cancer patients and 296 community controls. Three microsatellites, ESR1_TA, ESR2_CA and AR_CAG, in the ESR1, ESR2 and AR genes, respectively, were genotyped. Their repeat lengths were then analyzed as continuous and dichotomous variables. Analyses of continuous variables showed no association with breast cancer risk in either AA or NG at ESR1_TA; AA cases had shorter repeats in the long allele of ESR2_CA than AA controls (Mann-Whitney P= 0.036; logistic regression P = 0.04, OR= 0.91, 95% CI 0.83-1.00), whereas NG patients had longer repeats in the short allele than NG controls (Mann-Whitney P= 0.0018; logistic regression P= 0.04, OR= 1.06, 95% CI 1.00-1.11); and AA cases carried longer repeats in the short allele of AR_CAG than AA controls (Mann-Whitney P= 0.038; logistic regression P = 0.03, OR= 1.08, 95% CI 1.01-1.15). When allele sizes were categorized as dichotomous variables, we discovered that women with two long alleles of ESR2_CA had increased risk of breast cancer (OR = 1.38, 95% CI 1.10-1.74; P = 0.006). This is the first study to investigate these three microsatellites in hormonal receptor genes in relation to breast cancer risk in an indigenous African population. After adjusting for multiple-testing, our findings suggest that ESR2_CA is associated with breast cancer risk in Nigerian women, whereas ESR1_TA and AR_CAG seem to have no association with the disease among African American or Nigerian women.

  15. Determination of dosimetric and kinetic features of gamma irradiated solid calcium ascorbate dihydrate using ESR spectroscopy

    NASA Astrophysics Data System (ADS)

    Tuner, H.

    2013-01-01

    Effects of gamma radiation on solid calcium ascorbate dihydrate were studied using electron spin resonance (ESR) spectroscopy. Irradiated samples were found to present two specific ESR lines with shoulder at low and high magnetic field sides. Structural and kinetic features of the radicalic species responsible for experimental ESR spectrum were explored through the variations of the signal intensities with applied microwave power, variable temperature, high-temperature annealing and room temperature storage time studies. Dosimetric potential of the sample was also determined using spectrum area and measured signal intensity measurements. It was concluded that three radicals with different spectroscopic and kinetic features were produced upon gamma irradiation.

  16. {beta}-decay study of {sup 77}Cu

    SciTech Connect

    Patronis, N.; De Witte, H.; Gorska, M.; Huyse, M.; Kruglov, K.; Pauwels, D.; Van de Vel, K.; Van Duppen, P.; Van Roosbroeck, J.; Thomas, J.-C.; Materna, T.; Mathieu, L.; Serot, O.

    2009-09-15

    A {beta}-decay study of {sup 77}Cu has been performed at the ISOLDE mass separator with the aim to deduce its {beta}-decay properties and to obtain spectroscopic information on {sup 77}Zn. Neutron-rich copper isotopes were produced by means of proton- or neutron-induced fission reactions on {sup 238}U. After the production, {sup 77}Cu was selectively laser ionized, mass separated, and sent to different detection systems where {beta}-{gamma} and {beta}-n coincidence data were collected. We report on the deduced half-live, decay scheme, and possible spin assignment of {sup 77}Cu.

  17. High-frequency ESR spectra of the type Ib synthetic diamond and nanodiamond at low temperatures

    NASA Astrophysics Data System (ADS)

    Khatsko, E.; Kobets, M.; Dergachev, K.; Kulbickas, A.; Rasteniene, L.; Vaisnoras, R.

    2013-12-01

    The ESR absorption spectra on paramagnetic centers in the type Ib bulk diamond and nanodiamond powder were studied before and after irradiation with high energy electrons (2 MeV) for a wide range of frequencies (70-120 GHz) and temperatures (4.2-90 K). The absorption lines related to the nickel-ion growth catalyst Ni1+ and single nitrogen paramagnetic center N0 were observed in the ESR spectrum of bulk diamond. In the nanodiamond, the absorption lines of the paramagnetic centers with dangling bonds on the surface of the nanodiamond crystallites (surface defects) and the sidelines related to the hyperfine interaction were observed in the ESR spectra.

  18. 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.

  19. E.s.r. study of the post-radiolysis growth of spin-trapped radicals in gamma-irradiated aqueous solutions of thymine.

    PubMed

    Joshi, A; Moss, H; Riesz, P

    1978-08-01

    The post-irradiation growth of the spin-adduct nitroxide radical produced by the addition of the thymine--OD radical to t-nitrosobutane (tNB) in gamma-irradiated, de-aerated D2O solutions was investigated by e.s.r. The thymine--OD radical was formed by the addition of an OD radical to the C(5) position of thymine. Growth reached a greater maximum value and was more rapid with increasing dose. At a fixed dose, growth was also greater and more rapid if oxygen was present after gamma-radiolysis. The addition of a second radical to the spin-adduct nitroxide during radiolysis to give a diamagnetic intermediate, which can regenerate the spin-adduct radical during storage in air-free and in air-saturated solutions at room temperature, was inferred to be responsible for post-irradiation growth. U.V. photolysis at 260-280 nm of a solution containing the diamagnetic intermediate rapidly regenerates the spin-adduct nitroxide. The longer lifetime of the diamagnetic intermediate in oxygen-free solutions may be relevant to an understanding of the anoxic sensitization by nitroxides in cellular systems.

  20. Characterization and electrochemical studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes with 2-mercapto-3-substituted-quinazolin-4-one and 1,10-phenanthroline or ethylenediamine as ligands

    NASA Astrophysics Data System (ADS)

    Sawant, V. A.; Gotpagar, S. N.; Yamgar, B. A.; Sawant, S. K.; Kankariya, R. D.; Chavan, S. S.

    2009-04-01

    Some mixed ligand complexes of the type [M(L 1 or L 2)( phen or en)(H 2O)Cl], where M = Mn(II), Co(II), Ni(II) and Cu(II); HL 1 = 2-mercapto-quinazolin-4-one; HL 2 = 2-mercapto-3-phenyl-quinazolin-4-one; phen = 1,10-phenanthroline; en = ethylenediamine have been prepared. All complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, IR, UV-vis, ESR and powder X-ray diffraction studies. IR spectra of these complexes reveal that the complex formation occurred through both nitrogen and sulphur atoms. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for the complexes. The ESR spectral data of the Cu(II) complexes showed that the metal-ligand bonds have considerable covalent character. X-ray diffraction studies of Cu(II) complexes are used to elucidate the crystal structure. The electrochemical behaviour of mixed ligand Ni(II) complexes was studied which showed that complexes of phen appear at more positive potential as compared to those for corresponding en complexes.

  1. Characterization and electrochemical studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes with 2-mercapto-3-substituted-quinazolin-4-one and 1,10-phenanthroline or ethylenediamine as ligands.

    PubMed

    Sawant, V A; Gotpagar, S N; Yamgar, B A; Sawant, S K; Kankariya, R D; Chavan, S S

    2009-04-01

    Some mixed ligand complexes of the type [M(L(1) or L(2))(phen or en)(H(2)O)Cl], where M=Mn(II), Co(II), Ni(II) and Cu(II); HL(1)=2-mercapto-quinazolin-4-one; HL(2)=2-mercapto-3-phenyl-quinazolin-4-one; phen=1,10-phenanthroline; en=ethylenediamine have been prepared. All complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, IR, UV-vis, ESR and powder X-ray diffraction studies. IR spectra of these complexes reveal that the complex formation occurred through both nitrogen and sulphur atoms. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for the complexes. The ESR spectral data of the Cu(II) complexes showed that the metal-ligand bonds have considerable covalent character. X-ray diffraction studies of Cu(II) complexes are used to elucidate the crystal structure. The electrochemical behaviour of mixed ligand Ni(II) complexes was studied which showed that complexes of phen appear at more positive potential as compared to those for corresponding en complexes.

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

    PubMed

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

    2015-11-07

    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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Neutron ESR dosimetry through ammonium tartrate with low Gd content.

    PubMed

    Marrale, M; Brai, M; Longo, A; Panzeca, S; Tranchina, L; Tomarchio, E; Parlato, A; Buttafava, A; Dondi, D

    2014-06-01

    This paper continues analyses on organic compounds for application in neutron dosimetry performed through electron spin resonance (ESR). Here, the authors present the results obtained by ESR measurements of a blend of ammonium tartrate dosemeters and gadolinium oxide (5 % by weight). The choice of low amount of Gd is due to the need of improving neutron sensitivity while not significantly influencing tissue equivalence. A study of the effect of gadolinium presence on tissue equivalence was carried out. The experiments show that the neutron sensitivity is enhanced by more than an order of magnitude even with this small additive content. Monte Carlo simulations on the increment of energy release due to gadolinium presence were carried, and the results were in good agreement with the experimental data.

  8. Light-induced ESR centres in single crystal rutile

    NASA Astrophysics Data System (ADS)

    Hodgskiss, S. W.; Thorp, J. S.

    1983-04-01

    Electron spin resonance studies have been made on Verneuil-grown rutile single crystals, which were doped with a variety of transition gorup ions. Measurements were made at 9 GHz, both before and after UV irradiation, at temperatures in the range from 4.2 to 300 K. UV irradiation had two effects: (a) to affect the relative intensities of esr lines due to species already present, (b) to generate new esr spectra. Both effects are interpreted as representing a redistribution of charge amongst trapping centres. Seven UV generated centres have been identified and characterised in terms of their spin Hamiltonian parameters. Isochronal annealing techniques have been used to determine the ionisation temperatures of the traps. Observation of interactions and charge transfers between centres during isochronal annealing was used to determine the polarity and type of each centre.

  9. DAS28-CRP and DAS28-ESR cut-offs for high disease activity in rheumatoid arthritis are not interchangeable

    PubMed Central

    Fleischmann, Roy M; van der Heijde, Désirée; Gardiner, Philip V; Szumski, Annette; Marshall, Lisa; Bananis, Eustratios

    2017-01-01

    Background In most patients with rheumatoid arthritis (RA), Disease Activity Score 28-joint count C reactive protein (DAS28-CRP) is lower than DAS28 erythrocyte sedimentation rate (DAS28-ESR), suggesting that use of the DAS28-ESR cut-off to assess high disease activity (HDA) with DAS28-CRP may underestimate the number of patients with HDA. We determined the DAS28-CRP value corresponding to the validated DAS28-ESR cut-off for HDA. Methods Baseline data were pooled from 2 clinical studies evaluating etanercept (ETN) plus methotrexate (MTX) or MTX in early RA; DAS28-CRP and DAS28-ESR were obtained, allowing the determination of the DAS28-CRP HDA value best corresponding to the DAS28-ESR cut-off of >5.1. Results At baseline, as expected, fewer patients had HDA by DAS28-CRP than DAS28-ESR; DAS28-CRP>5.1 and DAS28-ESR>5.1 had only modest agreement (κ coefficients 0.45–0.54). Mean DAS28-CRP and DAS28-ESR were 5.7 and 6.2, respectively, in the ETN+MTX group (n=571), and 6.0 and 6.5 in the MTX group (n=262). A DAS28-CRP cut-off of 4.6 corresponded to a DAS28-ESR cut-off of 5.1. Conclusions We have shown that a DAS28-CRP of 4.6 corresponds to 5.1 for DAS28-ESR. Since this is substantially lower than the DAS28-ESR cut-off of 5.1, using 5.1 as the cut-off for DAS28-CRP underestimates disease activity in RA. Trial registration number NCT00195494; NCT00913458. PMID:28255449

  10. Atom probe study of Cu-poor to Cu-rich transition during Cu(In,Ga)Se2 growth

    NASA Astrophysics Data System (ADS)

    Couzinie-Devy, F.; Cadel, E.; Barreau, N.; Arzel, L.; Pareige, P.

    2011-12-01

    Atomic scale chemistry of polycrystalline Cu(In,Ga)Se2 (CIGSe) thin film has been characterized at key points of the 3-stage process using atom probe tomography. 3D atom distributions have been reconstructed when the layer is Cu-poor ([Cu]/([Ga] + [In]) < 1), Cu-rich ([Cu]/([Ga] + [In]) > 1), and at the end of the process. Particular attention has been devoted to grain boundary composition and Na atomic distribution within the CIGSe layer. Significant variation of composition is highlighted during the growing process, providing fundamental information helping the understanding of high efficiency CIGSe formation.

  11. 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.

  12. 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.

  13. The temperature during the high speed friction experiments estimated by ESR signals in quartz

    NASA Astrophysics Data System (ADS)

    Usami, T.; Toyoda, S.; Mizoguchi, K.; Shimamoto, T.; Hirose, T.

    2004-12-01

    ESR (electron spin resonance) dating method has been developed to obtain ages of quaternary geological events using calcite, aragonite, hydroxyapatite, and quartz. In natural quartz, paramagnetic (ESR sensitive) defects such as Al center (an Al atom replacing a Si, trapping an electronic hole) and Ti-Li center (a Ti atom replacing a Si, trapping an electron together with Li+ as a charge compensator) are stable for the geological time scale while they decay on heating according to the thermal activation processes. In the present study, we use these ESR signals as indicators of temperature during the high speed friction experiments. The present experiment will also tell the conditions of faulting which completely zero the ESR signals, which is necessary for ESR dating of faulting to work. The gamma ray irradiated quartz grains of 0.5 to 1 mm were sandwitched by two gabrro columns of 25 mm in diameter with a tephron sleeve. The friction expereiments were performed with a load of 30 kg and with speeds of 75 to 300 rotation per minutes. After removing the columns, the crushed quartz powder was divided into three parts, outer, intermediate, and inner parts. ESR measurements were performed by an ESR spectrometer, JEOL PX-2300, at 83-87K, with a microwave power of 5 mW, and with an modulation amplitude of 0.1 mT. The estimated temperatures are higher for outer part where the frictional speed is higher while lower for inside, with systematic difference for different ESR signals, when assuming that the temperature was constant during friction experiments. The temperatures will be estimated again, in the presentation, with considering the temperature change with time while friction experiments, also with taking into account the results of heating experiments.

  14. Chemical origin of the native ESR signals in thermally treated enamel and dentin

    NASA Astrophysics Data System (ADS)

    Bachmann, Luciano; Baffa, Oswaldo; Gomes, Anderson S. L.; Zezell, Denise M.

    2004-06-01

    Heating, crushing and exposure of dental enamel to sunlight and UV radiation can introduce paramagnetic signals similar to those following exposure to ionizing radiation. The objective of this work is to use infrared and electron spin resonance (ESR) spectra to study thermally treated enamel and dentin, and identify the chemical radical or mechanisms that produce these ambiguous ESR signals. Non-irradiated bovine teeth were used. ESR spectroscopy was performed in the X band and the infrared spectroscopy was performed on a FTIR spectrometer operating between 4000 cm -1 and 400 cm -1. The results show ESR signals in dentin heated at temperatures between 100°C and 1000°C and in enamel heated at temperatures ranging from 250°C to 1000°C. The ESR signal formed after heat treatment below 400°C could be assigned to degradation products of the organic material, while the ESR signals that predominate in tissues heated between 500°C and 900°C show a maximum amplitude at 750°C and could be assigned to the cyanate ion (NCO -).

  15. Electronic structure of CuTPP and CuTPP(F) complexes: a combined experimental and theoretical study II.

    PubMed

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

    2016-09-28

    The unoccupied electronic structure of thick films of tetraphenylporphyrin and tetrakis(pentafluorophenyl)porphyrin Cu(ii) complexes (hereafter, CuTPP and CuTPP(F)) deposited on Au(111) has been studied by combining the outcomes of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy with those of spin-unrestricted time-dependent density functional (TD-DFT) calculations carried out either within the scalar relativistic zeroth order regular approximation (ZORA) framework (C, N and F K-edges) or by using the Tamm-Dancoff approximation coupled to ZORA and including spin-orbit effects (Cu L2,3-edges). Similarly to the modelling of NEXAFS outcomes pertaining to other Cu(ii) complexes, the agreement between theory and experiment is more than satisfactory, thus confirming the open-shell TD-DFT to be a useful tool to look into NEXAFS results pertinent to Cu(ii) compounds. The combined effect of metalation and phenyl (Ph) fluorine decoration is found to favour an extensive mixing between (Ph)σ* and pristine porphyrin macrocyle (pmc) (pmc)π* virtual levels. The lowest lying excitation in the C and N K-edge spectra of both CuTPP and CuTPP(F) is associated with a ligand-to-metal-charge-transfer transition, unambiguously revealed in the (CuTPP)N K-edge spectral pattern. Moreover, the comparison with literature data pertaining to the modelling of the (Cu(II))L2,3 features in the phthalocyanine-Cu(ii) (CuPc) complex provided further insights into how metal-to-ligand-charge-transfer transitions associated with excitations from 2p(Cu(II)) AOs to low-lying, ligand-based π* MOs may contribute to the Cu(ii) L2,3-edge intensity and thus weaken its believed relationship with the Cu(ii)-ligand symmetry-restricted covalency. Despite the coordinative pocket of CuTPP/CuTPP(F) mirroring CuPc, the ligand-field strength exerted by the phthalocyanine ligand on the Cu(ii) centre is experimentally found and theoretically confirmed to be slightly stronger than that experienced by Cu

  16. Microstructure Characterization and Corrosion Resistance Behavior of New Cobalt-Free Maraging Steel Produced Through ESR Techniques

    NASA Astrophysics Data System (ADS)

    Seikh, Asiful H.; Halfa, Hossam; Baig, Muneer; Khan, Sohail M. A.

    2017-03-01

    In this study, two different grades (M23 and M29) of cobalt-free low nickel maraging steel have been produced through electroslag remelting (ESR) process. The corrosion resistance of these ESR steels was investigated in 1 M H2SO4 solution using linear potentiodynamic polarization (LPP) and electrochemical impedance spectroscopy (EIS) techniques. The experiments were performed for different immersion time and solution temperature. To evaluate the corrosion resistance of the ESR steels, some significant characterization parameters from LPP and EIS curves were analyzed and compared with that of conventional C250 maraging steel. Irrespective of measurement techniques used, the results show that the corrosion resistance of the ESR steels was higher than the C250 steel. The microstructure of ESR steels was composed of uniform and well-distributed martensite accompanied with little amount of retained austenite in comparison with C250 steel.

  17. 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.

  18. 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.

  19. In situ high-resolution transmission electron microscopy study of interfacial reactions of Cu thin films on amorphous silicon

    NASA Astrophysics Data System (ADS)

    Lee, Sung Bo; Choi, Duck-Kyun; Phillipp, Fritz; Jeon, Kyung-Sook; Kim, Chang Kyung

    2006-02-01

    Interfacial reactions of Cu with amorphous silicon (a-Si) in the Cu /a-Si/glass system are studied by in situ high-resolution transmission electron microscopy at 550°C. Various Cu silicides, such as η-Cu3Si, Cu15Si4, and Cu5Si, and Cu particles are observed. The formation of the Cu particles can be attributed to a heating effect from electron beam irradiation. Around the Cu silicides, crystallization of a-Si occurs. Around the Cu particles, however, crystallization does not occur. Crystallization appears to be enhanced by Cu dissolved in a-Si.

  20. 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.

  1. Kinetics, prognostic and predictive values of ESR1 circulating mutations in metastatic breast cancer patients progressing on aromatase inhibitor

    PubMed Central

    Clatot, Florian; Perdrix, Anne; Augusto, Laetitia; Beaussire, Ludivine; Delacour, Julien; Calbrix, Céline; Sefrioui, David; Viailly, Pierre-Julien; Bubenheim, Michael; Moldovan, Cristian; Alexandru, Cristina; Tennevet, Isabelle; Rigal, Olivier; Guillemet, Cécile; Leheurteur, Marianne; Gouérant, Sophie; Petrau, Camille; Théry, Jean-Christophe; Picquenot, Jean-Michel; Veyret, Corinne; Frébourg, Thierry; Jardin, Fabrice

    2016-01-01

    Purpose To assess the prognostic and predictive value of circulating ESR1 mutation and its kinetics before and after progression on aromatase inhibitor (AI) treatment. Patients and methods ESR1 circulating D538G and Y537S/N/C mutations were retrospectively analyzed by digital droplet PCR after first-line AI failure in patients treated consecutively from 2010 to 2012 for hormone receptor-positive metastatic breast cancer. Progression-free survival (PFS) and overall survival (OS) were analyzed according to circulating mutational status and subsequent lines of treatment. The kinetics of ESR1 mutation before (3 and 6 months) and after (3 months) AI progression were determined in the available archive plasmas. Results Circulating ESR1 mutations were found at AI progression in 44/144 patients included (30.6%). Median follow-up from AI initiation was 40 months (range 4-94). The median OS was decreased in patients with circulating ESR1 mutation than in patients without mutation (15.5 versus 23.8 months, P=0.0006). The median PFS was also significantly decreased in patients with ESR1 mutation than in patients without mutation (5.9 vs 7 months, P=0.002). After AI failure, there was no difference in outcome for patients receiving chemotherapy (n = 58) versus non-AI endocrine therapy (n=51) in patients with and without ESR1 mutation. ESR1 circulating mutations were detectable in 75% of all cases before AI progression, whereas the kinetics 3 months after progression did not correlate with outcome. Conclusion ESR1 circulating mutations are independent risk factors for poor outcome after AI failure, and are frequently detectable before clinical progression. Interventional studies based on ESR1 circulating status are warranted. PMID:27801670

  2. 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.

  3. Study of Substitution of Zn FOR Cu in YBa2Cu3O7 System

    NASA Astrophysics Data System (ADS)

    Sharma, P. K.; Samariya, A.; Dhawan, M. S.; Singhal, R. K.

    The polycrystalline YBa2(Cu1-XZnX)3O7-δ samples (x=0.0 to 0.06) were synthesized and studied using X Ray diffraction, titration, resistivity, magnetization and X ray photoelectron spectroscopy (XPS). Results show that O2 stoichiometry (δ) changes on Zn substitution which affects their normal state resistivity as well as the TC. Zn also induces local magnetic moment as evidenced from magnetization results. A combination of change in O2 stoichiometry and magnetic pair breaking is found to be responsible for a rapid suppression of superconductivity.

  4. Numerical study of the enhancement of heat transfer for hybrid CuO-Cu Nanofluids flowing in a circular pipe.

    PubMed

    Balla, Hyder H; Abdullah, Shahrir; Mohdfaizal, Wan; Zulkifli, Rozli; Sopian, Kamaruzaman

    2013-01-01

    A numerical simulation model for laminar flow of nanofluids in a pipe with constant heat flux on the wall was built to study the effect of the Reynolds number on convective heat transfer and pressure loss. The investigation was performed for hybrid nanofluids consisting of CuO-Cu nanoparticles and compared with CuO and Cu in which the nanoparticles have a spherical shape with size 50, 50, 50nm respectively. The nanofluids were prepared, following which the thermal conductivity and dynamic viscosity were measured for a range of temperatures (10 -60°C). The numerical results obtained were compared with the existing well-established correlation. The prediction of the Nusselt number for nanofluids agrees well with the Shah correlation. The comparison of heat transfer coefficients for CuO, Cu and CuO-Cu presented an increase in thermal conductivity of the nanofluid as the convective heat transfer coefficient increased. It was found that the pressure loss increases with an increase in the Reynolds number, nanoparticle density and particle volume fraction. However, the flow demonstrates enhancement in heat transfer which becomes greater with an increase in the Reynolds number for the nanofluid flow.

  5. 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.

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

    PubMed

    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, (1)H 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).

  8. 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).

  9. Graphene Growth on Cu Surface: A Theoretical Study

    NASA Astrophysics Data System (ADS)

    Li, Zhenyu; Wu, Ping; Zhang, Wenhua; Yang, Jinlong; Hou, J. G.; Electronic Structure Team at USTC Team

    2011-03-01

    Graphene is an important material with many unique properties and a great application potential. A promising way to produce wafer-size graphene is chemical vapor deposition (CVD) on metal surfaces. To improve sample quality, it is important to understand the atomic details during graphene CVD growth. In this talk, some relevant elementary processes on Cu surface have been studied from first principles. Although diffusion of atomic carbon on Cu (111) surface is almost barrierless, coalescence of carbon atoms on the surface is found to be hampered by an intermediate bridging-metal structure. The fact which makes things more complicated is that thermodynamic analysis indicates that the main species on the Cu surface during graphene growth is not the simplest atomic carbon. Therefore, CxHy species should be explicitly considered for initial stage growth of graphene on Cu surface. Partially supported by NSFC (20933006, 20803071, and 50721091), by MOE (FANEDD-2007B23 and NCET-08-0521), and by MOST(2006CB922004).

  10. Study of Dissolution Process of Solid Cu in Liquid Al

    NASA Astrophysics Data System (ADS)

    Chen, Shuying; Wu, Yang; Chang, Guowei; Zhu, Changxu; Li, Qingchun

    2016-09-01

    The dissolution process of solid Cu in liquid Al influences the compound quality directly when fabricating the copper cladding aluminum (CCA) composite castings utilizing the casting aluminum method. Dissolution rate of solid Cu is investigated utilizing the method of quenching rapidly. Effects of liquid Al temperature and the contact time between solid Cu and liquid Al on the dissolution rate of Cu are investigated; meanwhile, the dissolution mechanism of Cu is explored. Subsequently, the influences of processing parameters on the dissolution thickness of Cu are examined. The results indicate that chemical compounds, such as AlCu2, Cu5Al, CuAl2 and Cu2Al3, may form on the contact surface between solid Cu and liquid Al. These chemical compounds are contributed to decompose the solid Cu, Cu5Al exerts the greatest effect. The dissolution of Cu is affected by the contact time between solid Cu and liquid Al, temperature and cooling method of Cu plate. The dissolution of Cu cannot terminate immediately even though the Cu plate is cooled by the spray. The experimental results will provide a reference for controlling the composite layer thickness.

  11. ESR and TL investigations on gamma irradiated linden (Tilia vulgaris).

    PubMed

    Paksu, Ufuk; Aydaş, Canan; Yüce, Ülkü Rabia; Aydın, Talat; Polat, Mustafa; Engin, Birol

    2013-05-01

    Electron spin resonance (ESR) and thermoluminescence (TL) signals induced by gamma irradiation in linden (Tilia vulgaris) were studied for detection and dosimetric purposes. Before irradiation, linden leaf samples exhibit one singlet ESR signal centred at g = 2.0088. Besides this central signal, in spectra of irradiated linden samples, two weak satellite signals situated about 3 mT left (g = 2.0267) and right (g = 1.9883) were observed. Dose-response curves for the left satellite signal and the central single signal were constructed, and it was found that both of these curves can be described best by the combination of two exponential saturation functions. Variable temperature and fading studies at room temperature showed that the radiation-induced radicals in linden leaf samples are very sensitive to temperature. The stabilities of the left satellite (g = 2.0267) and the central single (g = 2.0088) signal at room temperature over a storage period of 126 days turned out to be best described by a sum of two first-order decay functions. The kinetic features of the left satellite signal were studied over the temperature range of 313-373 K. The results indicate that the isothermal decay curves of the left satellite ESR signal also proved to be best fitted by the combination of two first-order decay functions. Fading and annealing studies suggested the existence of two different radiation-induced free radical species. At the same time, Arrhenius plots evidenced two different kinetic regimes with two different activation energies. TL investigation of polyminerals from the linden samples allowed to discriminate clearly between irradiated and unirradiated samples even 75 days after irradiation.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. Effect of annealing on ESR characteristics of zirconia nanopowders with different impurity compositions

    NASA Astrophysics Data System (ADS)

    Bykov, I. P.; Brik, A. B.; Bagmut, N. N.; Kalinichenko, A. M.; Bevz, V. V.; Vereshchak, V. G.; Yastrabik, L.

    2009-06-01

    An ESR study is performed for four groups of zirconia nanopowder samples: nominally pure ZrO2 powders (first group), zirconia samples with Y2O3 and Sc2O3 impurities (second group), samples with different amounts of Cr2O3 (third group), and samples containing both Y2O3 and Cr2O3 (fourth group). The effect of annealing on ESR signals due to Zr3+ ions (sample groups 1 and 2) and Cr5+ ions (groups 3 and 4) is studied. It is established that, although the Zr3+ and Cr5+ ions have similar ESP characteristics, the annealing exerts different effects on ESR signals of these ions. Annealing in the temperature range 200-900°C leads to a monotonic increase in the amount of Zr3+ ions. Interestingly, the annealing temperature at which Zr3+ ions begin to generate ESR signals is different for samples with different impurity compositions. Unlike the Zr3+ ions, the annealing curves of the ESR signals due to the Cr5+ ions pass through an extremum at T = 500-600°C.

  19. Mechanical Property Characterization of ESR (Electroslag Remelted) 4353 Steel with a Comparison to ESR 4340 Steel

    DTIC Science & Technology

    1987-04-01

    IThe ESR 4J53 steel exhibits Charpy impact energy values of 12.4 ftib for 400 and 4504 tempers, which decrease to 9.2 ft&,jb for a 5000f temper as a...temperature or hard- ness, the ESR 4340 steel has greater Charpy impact energy and fracture tough- ness( KI )i. -w N .: UNCLASS IF I ED S Cul...pertinent for the consideration of high strength steels for Army applications include tensile -4 properties, hardness, Charpy V-notch impact energy

  20. Paraconductivity measurements and comparative studies of fluctuations in BiSrCaCuO, YBaCuO and YBaCuO with Gd substitution

    SciTech Connect

    Patapis, S.K.; Sideridis, L.; Apostolopoulos, G.; Ausloos, M.; Luo, H.L.; Politis, C.; Puig, T.; Pont, M.; Munoz, J.S.; Balachadran, U.

    1991-12-31

    Information concerning the dimensionality of the superconductive fluctuations in the new high temperature superconductors can be derived from the excess conductivity (or paraconductivity) near the transition temperature. Here the `lowering`` of the sample resistance in the same temperature regions is used for extraction of dimensionality and generally for comparative studies of the critical behaviour of three different samples such as YBa{sub 2}Cu{sub 3}O{sub 7}, Y{sub 0.8}Gd{sub 0.2}Ba{sub 2}Cu{sub 3}O{sub 7} and Bi{sub 0. 85}Pb{sub 0.15}SrCa{sub 1.2}Cu{sub 2}O{sub 6}. The experimental data of the three samples show a similar behaviour with some distinct differences depending rather on the ``metallurgical`` state of the material than the composition itself. A logarithmic behaviour is present for YBaCuO and Y(Gd)BaCuO samples not close to the critical temperature and, the most important, closer to {Tc} YBaCuO shows a fractal behaviour, observed for the first time, similar to the one of Bi-compound observed many times before.

  1. Paraconductivity measurements and comparative studies of fluctuations in BiSrCaCuO, YBaCuO and YBaCuO with Gd substitution

    SciTech Connect

    Patapis, S.K.; Sideridis, L.; Apostolopoulos, G. . Dept. of Physics); Ausloos, M. . Inst. de Physique); Luo, H.L. . Dept. of Electrical and Computer Engineering); Politis, C. . Inst. fuer Nukleare Festkoerperphysik); Puig, T.; Pont, M.; Munoz, J.S. (Univ

    1991-01-01

    Information concerning the dimensionality of the superconductive fluctuations in the new high temperature superconductors can be derived from the excess conductivity (or paraconductivity) near the transition temperature. Here the lowering'' of the sample resistance in the same temperature regions is used for extraction of dimensionality and generally for comparative studies of the critical behaviour of three different samples such as YBa{sub 2}Cu{sub 3}O{sub 7}, Y{sub 0.8}Gd{sub 0.2}Ba{sub 2}Cu{sub 3}O{sub 7} and Bi{sub 0. 85}Pb{sub 0.15}SrCa{sub 1.2}Cu{sub 2}O{sub 6}. The experimental data of the three samples show a similar behaviour with some distinct differences depending rather on the metallurgical'' state of the material than the composition itself. A logarithmic behaviour is present for YBaCuO and Y(Gd)BaCuO samples not close to the critical temperature and, the most important, closer to {Tc} YBaCuO shows a fractal behaviour, observed for the first time, similar to the one of Bi-compound observed many times before.

  2. 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)

  3. ESR dating of quartz extracted from quaternary and neogene sediments: method, potential and actual limits

    NASA Astrophysics Data System (ADS)

    Laurent, M.; Falguères, C.; Bahain, J. J.; Rousseau, L.; Van Vliet Lanoé, B.

    ESR dating of fluvial, fluvio-marine and beach sediment has been tested using the Al centre in quartz grains from a basin and fossil beaches located around the Manche Channel. Dating was performed in conjunction with sedimentological, stratigraphical and neotectonical studies. The technical basis of the method is presented in the light of the study made on recent and fossil sediment in order to establish a procedure for the determination of the palaeodose. The application on a Neogene Basin samples allows to push back the dating ESR limits. Results show that ESR dating of sediment can provide chronozons which are necessary to the uderstanding of the history of a basin where classical chronological markers do not exist.

  4. 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.

  5. 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.

  6. Determination of the Transverse Properties of ESR 4340 Steel.

    DTIC Science & Technology

    1980-09-01

    PROPERTIES OF ESR 4340 STEEL SEPTEMBER 1980 D TIC ELECTE John T. Berry JAN 2 2 1981, School of Mechanical Engineering 0 Georgia Institute of Technology...of the Transverse Properties of ESR 4340 Steel Covering period from August 3, 1978 to June 20, 1980. DATED: June 20, 1980 John T. Berry S. Peter Kezios...the plates, a thorough investigation was performed with respect to fabricating and testing AISI 4340 steel DLT bars. Materials from previous ESR 4340

  7. Study of EPR/ESR Dosimetry in Fingernails as a Method for Assessing Dose of Victims of Radiological Accidents/Incidents

    DTIC Science & Technology

    2008-06-17

    biodosimetry, fluorescence in situ hybridization (FISH), thermoluminescence (TL), and optically stimulated luminescence (OSL) [1]. EPR retrospective studies...Gammacell 40 Cesium 137 irradiator. C-2. EXPERIMENTAL DESIGN: 1) Several thermoluminescent detectors (TLDs), DT-702/PD, were irradiated at

  8. Co(II), Ni(II) and Cu(II) complexes with coumarin-8-yl Schiff-bases: Spectroscopic, in vitro antimicrobial, DNA cleavage and fluorescence studies

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

    A new series of Co(II), Ni(II) and Cu(II) complexes of the type ML·2H 2O of Schiff-bases derived from m-substituted thiosemicarbazides and 8-acetyl-7-hydroxy-4-methylcoumarin have been synthesized and characterized by spectroscopic studies. Schiff-bases exhibit thiol-thione tautomerism wherein sulphur 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, FAB-mass, ESR and fluorescence), magnetic and thermal studies. The low molar conductance values in DMF indicate that, the metal complexes are non-electrolytes. The cyclic voltammetric studies suggested that, the Cu(II) and Ni(II) complexes are of single electron transfer quasi-reversible nature. The Schiff-bases and its metal complexes have been evaluated for their in vitro antibacterial ( Escherichia coli, Staphilococcus aureus, Bascillus subtilis and Salmonella typhi) and antifungal activities ( Candida albicans, Cladosporium and Aspergillus niger) by MIC method. The Schiff-base I and its metal complexes exhibited DNA cleavage activity on isolated DNA of A. niger.

  9. 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.

  10. Co(II), Ni(II) and Cu(II) complexes with coumarin-8-yl Schiff-bases: spectroscopic, in vitro antimicrobial, DNA cleavage and fluorescence studies.

    PubMed

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

    2011-09-01

    A new series of Co(II), Ni(II) and Cu(II) complexes of the type ML·2H2O of Schiff-bases derived from m-substituted thiosemicarbazides and 8-acetyl-7-hydroxy-4-methylcoumarin have been synthesized and characterized by spectroscopic studies. Schiff-bases exhibit thiol-thione tautomerism wherein sulphur 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, FAB-mass, ESR and fluorescence), magnetic and thermal studies. The low molar conductance values in DMF indicate that, the metal complexes are non-electrolytes. The cyclic voltammetric studies suggested that, the Cu(II) and Ni(II) complexes are of single electron transfer quasi-reversible nature. The Schiff-bases and its metal complexes have been evaluated for their in vitro antibacterial (Escherichia coli, Staphilococcus aureus, Bascillus subtilis and Salmonella typhi) and antifungal activities (Candida albicans, Cladosporium and Aspergillus niger) by MIC method. The Schiff-base I and its metal complexes exhibited DNA cleavage activity on isolated DNA of A. niger.

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

    PubMed

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

    2015-02-25

    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, (1)H NMR, (13)C 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.

  12. An investigation of the kinetics of the mesophase transformations in petroleum pitch by the ESR method

    SciTech Connect

    Samoilov, V.M.; Frolov, V.I.; Kotosonov, A.S.; Ostronov, B.G.; Rumyantsev, S.M.

    1983-01-01

    The amount of ..cap alpha../sub 1/ fraction, the concentration of paramagnetic centers, and the width of the line of the ESR signal have been determined for samples of mesophase pitches obtained by treating an initial petroleum pitch at 400-440/sup 0/C. The applicability of the ESR method for studying the kinetics and mechanism of the process of mesophase transformations has been shown. From the change in the parameters studied the rate constants and activation energies of the processes of the formation and growth of the aromatic regions of polyconjugation and of the accumulation of mesophase have been calculated.

  13. Calorimetric studies of Cu-Li, Li-Sn, and Cu-Li-Sn.

    PubMed

    Fürtauer, S; Tserenjav, E; Yakymovych, A; Flandorfer, H

    2013-06-01

    Integral molar enthalpies of mixing were determined by drop calorimetry for Cu-Li-Sn at 1073 K along five sections xCu/xSn ≈ 1:1, xCu/xSn ≈ 2:3, xCu/xSn ≈ 1:4, xLi/xSn ≈ 1:1, and xLi/xSn ≈ 1:4. The integral and partial molar mixing enthalpies of Cu-Li and Li-Sn were measured at the same temperature, for Li-Sn in addition at 773 K. All binary data could be described by Redlich-Kister-polynomials. Cu-Li shows an endothermic mixing effect with a maximum in the integral molar mixing enthalpy of ∼5300 J · mol(-1) at xCu = 0.5, Li-Sn an exothermic minimum of ∼ -37,000 J · mol(-1) at xSn ∼ 0.2. For Li-Sn no significant temperature dependence between 773 K and 1073 K could be deduced. Our measured ternary data were fitted on the basis of an extended Redlich-Kister-Muggianu model for substitutional solutions. Additionally, a comparison of these results to the extrapolation model of Chou is given.

  14. Dislocation kinematics: a molecular dynamics study in Cu

    NASA Astrophysics Data System (ADS)

    Oren, E.; Yahel, E.; Makov, G.

    2017-02-01

    The kinematics and kinetics of edge and screw dislocations in FCC materials were studied by molecular dynamics, with Cu as a case study. It was found that with increasing stress screw dislocations enter into the transonic regime continuously and that they remain stable up to a velocity of about 2.2 km s-1. Edge dislocations are limited by the transverse sound velocity at low stresses and discontinuously cross into the transonic regime at higher stresses. For sufficiently long edge dislocations, the subsonic-transonic transition is initiated by an athermal nucleation process. Finally, an expression for the velocity dependence of the dislocation mobility was derived.

  15. 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.

  16. Micro-Raman Study of Orientation Effects of CuxSe-Crystallites on Cu-rich CuGaSe2 Thin Films

    NASA Astrophysics Data System (ADS)

    Xue, C.; Papadimitriou, D.; Raptis, Y. S.; Richter, W.; Esser, N.; Siebentritt, S.; Lux-Steiner, M. Ch.

    2004-08-01

    The structural properties of copper selenide (CuxSe), formed as a secondary phase on the surface of CuGaSe2 films grown under Cu-rich conditions on GaAs (100) substrates, were studied by micro-Raman spectroscopy. Raman bands at 45 and 263cm-1, observed on crystallites dispersed on the CuGaSe2 film, are in agreement with the Raman modes of CuSe and Cu2Se. Polarization- and angular-dependent micro-Raman measurements reveal that the CuxSe-crystallites are grown with a preferential orientation on the CuGaSe2 surface.

  17. Near-IR and ESR studies of the radical anions of C60 and C70 in the system fullerene-primary amine

    NASA Astrophysics Data System (ADS)

    Lobach, A. S.; Goldshleger, N. F.; Kaplunov, M. G.; Kulikov, A. V.

    1995-09-01

    The excited state proton transfer rate of 4-hydroxy-1-naphthalenesulphonate has been studied in methanol-water and ethanol-water mixtures. The lifetimes of the probe are measured at six different temperatures between 5 and 60°C. The decay is single exponential in the long time regime and proton transfer rates have been found to increase with the square of the concentration of water in alcohol-water mixtures. The decay has been explained by a new model proposing a water dimer to be the effective proton acceptor in the proton transfer process.

  18. 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.

  19. 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

  20. Evaluation of the Relative Hydrogen Embrittlement Susceptibility of ESR 4340 and Its Heat Treat Distortion Properties

    DTIC Science & Technology

    1982-09-01

    4340 Steel Heat treatment ESR Steel Helicopters...embrittlement suscepti- bility of remelted 4340 steel with ESR and VAR methods has been completed. The issue of ESR’s susceptibility to hydrogen...strength (above 260 Ksi) 4340 ESR steel is used in these applications because of 4340 ESR’s demonstrated supe- rior ballistic tolerance. Three

  1. Elaborated studies for the ligitional behavior of thiouracil derivative towards Ni(II), Pd(II), Pt(IV), Cu(II) and UO2 ² ions.

    PubMed

    Abou-Melha, Khlood Saad

    2012-11-01

    A synthesis of new thiouracil derivative was carried out and deliberately investigated. A new series of complexes was prepared using Ni(II), Pd(II), Pt(IV), Cu(II) and UO(2)(+2) ions. IR spectral data proposed the coordination mod of the ligand towards each metal ion and displays the binegative pentadentate mod as the maximum mod of coordination obtained with Ni(II) and Cu(II) complexes. (1)HNMR spectrum of UO(2)(+2) complex in comparing with the free ligand spectrum supports the binegative appearance of the coordinated ligand through the ionization of CO and CS groups. The electronic spectral data as well as the magnetic moment measurements are coincide with each others to propose the square-planar geometry with Ni(II), Pd(II) and Cu(II) complexes and octahedral geometry with the others. ESR spectrum of Cu(II) complex displays axially symmetric g tensor parameters with g(11)>g(⊥)>2.0023 indicating that the [Formula: see text] orbital as a ground state with the square-planar geometry. The TG analysis for all isolated complexes were carried out to assert about the presence of water molecules physically or chemically attached with the central atom. The biological study was carried out against different microorganisms as gram negative, gram positive and fungi. The comparable data display the relative priority of Ni(II) complex in comparing with others against all organisms but, the other complexes display activity by the same with the free ligand.

  2. 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.

  3. In situ radiolysis time-resolved ESR studies of spin trapping by DMPO: Re-evalution of hydroxyl radical and hydrated electron trapping rates and spin adduct yields

    SciTech Connect

    Madden, K.P.; Taniguchi, Hitoshi

    1996-05-02

    The second-order rate constants for the reaction of 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) with radiolytically produced hydroxyl radicals and hydrated electrons have been measured in aqueous solution by direct observation of spin adduct initial yield using time-resolved electron spin resonance. The rate constants are 2.8 x 10{sup 9} mol{sup -1} dm{sup 3} S{sup -1} for the DMPO-hydroxyl radical reaction and 3.2 x 10{sup 9} mol{sup -1} dm{sup 3} s{sup -1} for the reaction of DMPO and hydrated electron, using sodium formate and chloroacetic acid as competitive scavengers of the hydroxyl radical and hydrated electron, respectively. The hydrated electron-DMPO competition study determined the fraction of DMPO-H produced directly from radiolytically produced hydrogen atoms as 0.082 of the total DMPO-H yield, indicating that approximately half of the hydrogen atoms react with DMPO to produce non-aminoxyl products. The fraction of the total hydroxyl radical yield leading to DMPO-OH spin adduct was determined to be 0.94, using the bleach of 2,2,6,6-tetramethylpiperidone-N-oxyl by carbon dioxide radical anion as a reference standard. 36 refs., 8 figs., 1 tab.

  4. Electron spin resonance (ESR) studies on the formation of roasting-induced antioxidative structures in coffee brews at different degrees of roast.

    PubMed

    Bekedam, E Koen; Schols, Henk A; Cämmerer, Bettina; Kroh, Lothar W; van Boekel, Martinus A J S; Smit, Gerrit

    2008-06-25

    The antioxidative properties of coffee brew fractions were studied using electron spin resonance spectroscopy using 2,2,6,6-tetramethyl-1-piperidin-1-oxyl (TEMPO) and Fremy's salt (nitrosodisulfonate) as stabilized radicals. TEMPO was scavenged by antioxidants formed during roasting and not by chlorogenic acid, whereas Fremy's salt was scavenged by all antioxidants tested including chlorogenic acid. The stabilized radical TEMPO allowed the exclusive measurement of roasting-induced antioxidants. The roasting-induced antioxidant activity of coffee brews increased with increasing degree of roast, and most of these antioxidants were formed during the initial roasting stage. The majority of these roasting-induced antioxidants were present in the high molecular weight fractions, indicating that the formation of these antioxidants preferably occurs at specific high molecular weight structures, likely being arabinogalactan and/or protein moieties which might be part of the melanoidin complex. It was found that chlorogenic acids most probably do not lose their antioxidant activity and phenolic characteristics upon incorporation in coffee melanoidins. The parameter fast reacting antioxidants (FRA) was introduced as an alternative for the antioxidative potential. FRA levels showed that coffee fractions rich in roasting-induced antioxidants exposed their antioxidant activity relatively slowly, which must be a consequence of its complex structure. Finally, the melanoidin content and the roasting-induced antioxidant activity showed a positive and linear correlation for the coffee brew fractions, showing that roasting-induced antioxidants are present within melanoidins. This is the first time that the formation of roasting-induced antioxidants could be directly correlated with the extent of Maillard reaction and melanoidin formation in a complex product such as coffee.

  5. High temperature neutron powder diffraction study of the Cu12Sb4S13 and Cu4Sn7S16 phases

    NASA Astrophysics Data System (ADS)

    Lemoine, Pierric; Bourgès, Cédric; Barbier, Tristan; Nassif, Vivian; Cordier, Stéphane; Guilmeau, Emmanuel

    2017-03-01

    Ternary copper-containing sulfides Cu12Sb4S13 and Cu4Sn7S16 have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu12Sb4S13 and Cu4Sn7S16 phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu12Sb4S13 decomposes above ≈792 K into Cu3SbS3, and (ii) Cu4Sn7S16 decomposes above ≈891 K into Sn2S3 and a copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu3SnS4 stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu12Sb4S13 are in fair agreement with recent published data, the decomposition behavior of Cu4Sn7S16 differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu4Sn7S16 and tetrahedrite Cu12Sb4S13 phases at 300 K, and for the high temperature form of skinnerite Cu3SbS3 at 843 K.

  6. 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.

  7. 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.

  8. Application of 67Cu Produced by 68Zn(n,n'p+d)67Cu to Biodistribution Study in Tumor-Bearing Mice

    NASA Astrophysics Data System (ADS)

    Sugo, Yumi; Hashimoto, Kazuyuki; Kawabata, Masako; Saeki, Hideya; Sato, Shunichi; Tsukada, Kazuaki; Nagai, Yasuki

    2017-02-01

    67Cu produced by the 68Zn(n,n'p+d)67Cu reaction was used for the first time to determine the biodistribution of 67CuCl2 in colorectal tumor-bearing mice. A high uptake of 67Cu was observed in the tumor as well as in the liver and kidney, which are the major organs for copper metabolism. The result showing 67Cu accumulation in the tumor suggests that 67CuCl2 can be a potential radionuclide agent for cancer radiotherapy. It should also encourage further studies on the therapeutic effect on small animals using an increased dose of 67Cu produced by the 68Zn(n,n'p+d)67Cu reaction using presently available intense neutrons.

  9. Synthesis, spectral characterization and microbiological studies of Co(II), Ni(II) and Cu(II) complexes with some novel 20-membered macrocyclic hydrazino-1,2,4-triazole Schiff bases.

    PubMed

    Avaji, Prakash Gouda; Patil, Sangamesh Amarappa

    2009-02-01

    A series of Co(II), Ni(II) and Cu(II) complexes have been synthesized by template condensation of 2,6-diformyl-4-methylphenol and 3-substituted-4-amino-5-hydrazino-1,2,4-triazole with CoCl(2).6H(2)O, NiCl(2).6H(2)O and CuCl(2).2H(2)O chlorides in 2 + 2+2 molar ratio in ethanol. These complexes were characterized by elemental analyses, magnetic susceptibility, molar conductance, spectral (IR, Uv-Vis, ESR, (1)H NMR and FAB-mass), thermal, fluorescence and solid-state DC electrical conductivity studies. The observed molar conductance values indicate that they are non-electrolytes. Elemental analyses suggest the complexes to have 2:1 stoichiometry of the type [M(2)LX(2)] 2H(2)O (M = Co(II) & Cu(II), L = L(I)-L(IV) and X = Cl) and [Ni(2)LX(2)2H(2)O] 2H(2)O. The solid state DC electrical conductivity showed that the complexes were semiconducting. All the Schiff bases and their Co(II), Ni(II) and Cu(II) complexes were evaluated for their microbiological properties and some compounds showed promising results.

  10. Criticality accident dosimetry with ESR spectroscopy.

    PubMed

    d'Errico, F; Fattibene, P; Onori, S; Pantaloni, M

    1996-01-01

    The suitability of the ESR alanine and sugar detectors for criticality accident dosimetry was experimentally investigated during an intercomparison of dosimetry techniques. Tests were performed irradiating detectors both free-in-air and on-phantom during controlled critcality excursions at the SILENE reactor in Valduc, France. Several grays of absorbed dose were imparted in neutron gamma-ray fields of various relative intensities and spectral distributions. Analysed results confirmed the potential of these systems which can immediately provide an acute dose assessment with an average underestimate of 30%in the various fields. This performance allows for the screening of severely exposed individuals and meets the IAEA recommendations on the early estimate of accident absorbed doses.

  11. 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.

  12. Experimental Study of Copper Isotope Fractionation During the Formation of Cu and Cu-Fe Sulfides in Aqueous Solutions at 40-200 °C

    NASA Astrophysics Data System (ADS)

    Pekala, M.; Asael, D.; Butler, I. B.; Matthews, A.; Rickard, D.

    2009-12-01

    Natural Cu and Cu-Fe sulfides show significant Cu fractionation. In order to interpret these data an improved understanding of the major Cu isotope fractionation processes is required. Here we report laboratory experiments aimed at elucidating processes involved in Cu isotope distribution in Cu sulfides. Progressive replacement of Fe sulfides by Cu-Fe and Cu sulfides has been widely reported from a range of magmatic, hydrothermal and sedimentary deposits, and may sometimes lead to economically relevant Cu accumulations such as in the Kupferschiefer of SW Poland [1]. This replacement sequence is commonly observed in deep sea floor hydrothermal vents where massive Cu-Fe sulfide mineralisation is found [5,6]. Experimental investigations [2,3,4] have demonstrated that this type of mineral replacement is developed during the reaction of Fe sulfides (pyrrhotite and pyrite) with Cu(II)-rich aqueous solutions. Fractionation of Cu isotopes during the reaction of Fe sulfides (natural crystals of pyrrhotite and pyrite) with Cu(II) sulfate solutions was studied under anoxic conditions. It was observed that the original Fe sulfides were replaced by Cu-Fe and Cu sulfides. The effect of temperature (40-200 °C) and reaction extent (10-100 %) were investigated. Cu isotope ratios were determined in the Cu(II) solutions and in the corresponding mineral phases by sector field multicollector inductively coupled plasma mass spectrometry. Measured Cu(II) solution-Cu sulfide fractionation factors (in excess of 2 ‰) show substantial Cu isotope fractionation accompanying the reaction of Fe sulfides with Cu(II) solutions. The data points to a kinetic fractionation process that favours the transfer of the lighter Cu isotope into the mineral phase. The extent of Cu isotope fractionation resulting from this alteration process is of a similar order to fractionation observed during direct CuS precipitation from Cu(II)aq and S(-II)aq [7]. This suggests that Cu(II)-Cu(I) reduction, that proceeds

  13. Experimental study of copper isotope fractionation during the formation of Cu and Cu-Fe sulfides in aqueous solutions at 40-200 °C.

    NASA Astrophysics Data System (ADS)

    Pekala, Marek; Asael, Dan; Butler, Ian B.; Matthews, Alan; Rickard, David

    2010-05-01

    Natural Cu and Cu-Fe sulfides show significant Cu fractionation. In order to interpret these data an improved understanding of the major Cu isotope fractionation processes is required. Here we report laboratory experiments aimed at elucidating processes involved in Cu isotope distribution in Cu sulfides. Progressive replacement of Fe sulfides by Cu-Fe and Cu sulfides has been widely reported from a range of magmatic, hydrothermal and sedimentary deposits, and may sometimes lead to economically relevant Cu accumulations such as in the Kupferschiefer of SW Poland [1]. This replacement sequence is commonly observed in deep sea floor hydrothermal vents where massive Cu-Fe sulfide mineralisation is found [2,3]. Experimental investigations [4,5,6] have demonstrated that this type of mineral replacement is developed during the reaction of Fe sulfides (pyrrhotite and pyrite) with Cu(II)-rich aqueous solutions. Fractionation of Cu isotopes during the reaction of Fe sulfides (natural crystals of pyrrhotite and pyrite) with Cu(II) sulfate solutions was studied under anoxic conditions. It was observed that the original Fe sulfides were replaced by Cu-Fe and Cu sulfides. The effect of temperature (40-200 °C) and reaction extent (10-100 %) were investigated. Cu isotope ratios were determined in the Cu(II) solutions and in the corresponding mineral phases by sector field multicollector inductively coupled plasma mass spectrometry. Measured Cu(II) solution-Cu sulfide fractionation factors (in excess of 2 permil) show substantial Cu isotope fractionation accompanying the reaction of Fe sulfides with Cu(II) solutions. The data points to a kinetic fractionation process that favours the transfer of the lighter Cu isotope into the mineral phase. The extent of Cu isotope fractionation resulting from this alteration process is of a similar order to fractionation observed during direct CuS precipitation from Cu(II)aq and S(-II)aq [7]. This suggests that Cu(II)-Cu(I) reduction, that

  14. Electron backscatter diffraction study of hexagonal boron nitride growth on Cu single-crystal substrates.

    PubMed

    Hite, Jennifer K; Robinson, Zachary R; Eddy, Charles R; Feigelson, Boris N

    2015-07-22

    Hexagonal boron nitride (h-BN) is an important material for the development of new 2D heterostructures. To enable this development, the relationship between crystal growth and the substrate orientation must be explored and understood. In this study, we simultaneously grew h-BN on different orientations of Cu substrates to establish the impact of substrate structure on the growth habit of thin h-BN layers. The substrates studied were a polycrystalline Cu foil, Cu(100), Cu(110), and Cu(111). Fourier transform grazing-incidence infrared reflection absorption spectroscopy (FT-IRRAS) was used to identify h-BN on copper substrates. X-ray photoelectron spectroscopy (XPS) was used to determine the effective thickness of the h-BN. Scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) were used to measure the morphology of the films and postgrowth crystal structure of the Cu substrates, respectively. Combining the SEM and EBSD images allowed for the correlation between h-BN film coverage and the crystal structure of Cu. It was found that the growth rate was inversely proportional to the surface free energy of the Cu surface, with Cu(111) having the most h-BN surface coverage. The Cu foil predominately crystallized with a (100) surface orientation, and likewise had a film coverage very close to the Cu(100).

  15. Weak ferromagnetic behavior, crystal structure, and electronic studies of novel [Cu(II)(Br)(PhCO 2)(Sp)] (Sp=(-)-sparteine) complex

    NASA Astrophysics Data System (ADS)

    Reyes-Ortega, Yasmi; Alcántara-Flores, José Luis; Hernández-Galindo, María del Carmen; Gutiérrez-Pérez, René; Ramírez-Rosales, Daniel; Bernès, Sylvain; Cabrera-Vivas, Blanca Martha; Durán-Hernández, Alejandro; Zamorano-Ulloa, Rafael

    2006-05-01

    Complex [Cu(II)(Br)(PhCO 2)(Sp)] 1 is obtained starting from copper(0), (-)-sparteine (sp) and benzoyl bromide. 1 Crystallizes in the monoclinic space group P2 1 with a=14.8857(11), b=8.9257(9), c=17.4456(14) Å, β=111.689(5)°, and Z=4. The UV-vis spectrum is characteristic of Cu(II) complexes with tetragonally distorted square pyramidal geometry. The far IR spectrum of 1 shows characteristic vibrations of Cu-Br (239 cm -1), Cu-N (437 cm -1) and Cu-O (466 cm -1) bonds. The 1H NMR broad chemical shifts of 1 integrated for a total of 31 protons and are typical of Cu(II) complexes. ESR spectra of polycrystalline 1 at 77 and 300 K show axial spectra with areas in the ratio A77/ A300=4.02, suggesting a very weak Cu-Cu ferromagnetic interaction. Complex 1-doped with Zn(II) gives hfs with hyperfine interaction constant value A∥=112.45×10 -4 cm -1. The magnetization vs temperature data in the 2-299 K range, show that cupric ion pairs interact through a small antiferromagnetic Heisenberg exchange energy— JS1· S2 with a ground singlet state S=0, separated by J=-1.3 cm -1 from the excited triplet state S=1. The sign of the very weak interchange interaction constant, J, does not agree with the ESR spectra areas ratio of 1 at 77 and 300 K, which is a more accurate quantification of the weak ferromagnetic interaction Cu-Cu through the space.

  16. 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...

  17. Study of the tolerance of Hippochaete ramosissimum to Cu stress.

    PubMed

    Liu, Dengyi; Li, Ying; Chu, Ling; Wang, Guanglin; Wang, Lilong

    2005-05-01

    We investigated the tolerance of Hippochaete ramosissimum and the changes in physiological metabolism following exposure to copper using pot experiments and analyzing plant physiology and biochemistry. The results showed that Cu tolerance in Hippochaete ramosissimum varied significantly between different populations; the tolerance of plants living in Cu polluted areas for extended periods of time exceeded that of plants living in unpolluted areas. SOD and POD activities in highly Cu tolerant plants increased noticeably following exposure to Cu. This indicates that maintaining and increasing the two kinds of protective enzyme activities are the primary foundations of plant tolerance. However, no change in CAT activity was demonstrated following Cu exposure. In summary, there existed considerable differences in physiological metabolism between different populationsof Hippochaete ramosissimum following exposure to Cu.

  18. 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.

  19. Torque magnetometry study of magnetically ordered state and spin reorientation in the quasi-one-dimensional S =1/2 Heisenberg antiferromagnet CuSb2O6

    NASA Astrophysics Data System (ADS)

    Herak, Mirta; Žilić, Dijana; Matković Čalogović, Dubravka; Berger, Helmuth

    2015-05-01

    The antiferromagnetically ordered state of the monoclinic quasi-one-dimensional S =1 /2 Heisenberg antiferromagnet CuSb2O6 was studied combining torque magnetometry with a phenomenological approach to magnetic anisotropy. This system is known to have a number of different twins in the monoclinic β phase, which differ in the orientation of the two CuO6 octahedra in the unit cell resulting in different orientation of magnetic axes with respect to crystal axes for each twin. We performed torque measurements in magnetic fields H ≤0.8 T on a sample where a certain type of twin was shown to be dominant by ESR spectroscopy. The measured data reveal that the easy axis is the crystallographic b axis for this sample. Phenomenological magnetocrystalline anisotropy energy invariant to crystal symmetry operations was used to model the spin axis direction in zero and finite magnetic fields. Our model reproduces the value of the spin-flop field HSF=1.25 T found in literature. A combination of this approach with our torque results shows that the spin axis will flop in the direction of the maximal value of measured g tensor when the magnetic field H >HSF is applied along the easy axis direction. Our analysis of magnetocrystalline anisotropy energy predicts two possibilities for the easy axis direction in this system, b or a , connected to different crystallographic twins that can be realized in CuSb2O6 . These results offer a possibility to reconcile the different reports of easy axis direction found in literature for this system and also nicely demonstrate how a combination of torque magnetometry and a phenomenological approach to magnetic anisotropy can be used to determine the value of the spin-flop field and the direction of spin axis in antiferromagnets in both H HSF by performing measurements in fields significantly smaller than HSF.

  20. 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.

  1. Low-Temperature Studies of CuFe2S3 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

    2016-12-01

    The resonance ^{63,65}Cu NMR spectra in the internal magnetic field in cubanite CuFe2S3 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 Cu7Fe_{14}S_{29}^n for cubanite and Cu9Fe_{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 Cu7Fe_{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 Cu9Fe_{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.

  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. 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.

  4. 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.

  5. 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

  6. 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.

  7. Microwave absorption studies on high-T sub c superconductors and related materials II; Electron spin resonance of DPPH coated on Y sub 1 Ba sub 2 Cu sub 3 O sub y as a probe of magnetic field variations

    SciTech Connect

    Sugawara, K.; Baar, D.J.; Shiohara, Y.; Tanaka, S. )

    1991-05-10

    This paper reports on the ESR linewidth ({Delta}{ital H}{sub p{bar p}}) of DPPH coated on the surface of powder specimens of Y{sub 1}Ba{sub 2}Cu{sub 3}O{sub y} studied under various magnetic field and temperature conditions. {Delta}{ital H}{sub p{bar p}} increases substantially with decreasing temperature in the field cooled case, whereas almost no linewidth broadening was found in the zero field cooled case. {Delta}{ital H}{sub p{bar p}} was found to be sensitive to the applied magnetic field. This effect was very pronounced at temperatures lower than 40 K, but decreased strongly with increasing temperature. The broadening of the resonance lineshape has been attributed to spatial and temporal variations of the fluxon distribution in the powder particles.

  8. 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.

  9. 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

  10. Double quantum coherence electron spin resonance on coupled Cu(II)-Cu(II) electron spins

    NASA Astrophysics Data System (ADS)

    Becker, James S.; Saxena, Sunil

    2005-10-01

    We demonstrate for the first time the ability to generate double quantum coherences (DQCs) for the case of Cu(II). We show that small splittings (˜7 MHz) from the Cu(II)-Cu(II) electron-electron magnetic dipolar interaction can be reliably resolved even though the inhomogeneously broadened Cu(II) linewidth is ˜2 GHz. A Cu(II)-Cu(II) distance of 2.0 nm was measured on a model peptide system, thus, demonstrating that distances on the nanometer scale may be measured using DQC electron spin resonance (ESR).

  11. ESR spectra of VO2+ ions adsorbed on calcium phosphates.

    PubMed

    Oniki, T; Doi, Y

    1983-07-01

    The ESR spectra of oxovanadium(IV) ions, (VO2+), adsorbed on hydroxyapatite(OHAp), fluorhydroxyapatite(FHAp), Mg-containing tricalcium phosphate(Mg-TCP), .octacalcium phosphate (OCP), dicalcium phosphate dihydrate (DCPD), and amorphous calcium phosphate(ACP) were measured at room temperature. The ESR parameters of VO2+ adsorbed on these compounds were slightly different from one another and accordingly, the ESR technique by use of VO2+ was useful for an analysis of the calcium phosphates precipitated from supersaturated solutions. The ESR parameters of VO2+ adsorbed on ACP and Mg-TCP were found to be very similar to each other, suggesting that ACP and TCP resemble each other in the structure of their crystal surfaces.

  12. Ferromagnetic properties of Cu-doped ZnS: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Yan, Huiyu; Li, Yuqi; Guo, Yanrui; Song, Qinggong; Chen, Yifei

    2011-02-01

    Using plane-wave pseudopotential (PWPP) method, the magnetism and spin-resolved electronic properties of Cu-doped ZnS system are studied. Our calculations indicate that ferromagnetic (FM) state is ground state in Cu-doped ZnS. The FM coupling strength in ZnS doping with Cu fluctuates with the variation of distance between two dopants and the fluctuation gets larger with increase in distance. Room temperature ferromagnetism can be observed in Cu-doped ZnS with high dopant concentration. Formation energy calculation implies that the clustering effect is not obvious in Cu-doped ZnS. Thus, Cu-doped ZnS can be a promising dilute magnetic semiconductor (DMS), which promises to be free of magnetic precipitates.

  13. EPR and optical absorption study of Cu2+ doped lithium sulphate monohydrate (LSMH) single crystals

    NASA Astrophysics Data System (ADS)

    Sheela, K. Juliet; Krishnan, S. Radha; Shanmugam, V. M.; Subramanian, P.

    2016-05-01

    EPR study of Cu2+ doped NLO active Lithium Sulphate monohydrate (Li2SO4.H2O) single crystals were grown successfully by slow evaporation method at room temperature. The principal values of g and A tensors indicate existence of orthorhombic symmetry around the Cu2+ ion. From the direction cosines of g and A tensors, the locations of Cu2+ in the lattice have been identified as interstitial site. Optical absorption confirms the rhombic symmetry and ground state wave function of the Cu2+ ion in a lattice as dx2-y2.

  14. Synthesis, physico-chemical investigations of Co(II), Ni(II) and Cu(II) complexes and their in vitro microbial, cytotoxic, DNA cleavage studies.

    PubMed

    Bagihalli, Gangadhar B; Patil, Sangamesh A

    2010-06-01

    A series of metal complexes of cobalt(II), nickel(II), and copper(II) have been synthesized with newly derived biologically active ligands. These ligands were synthesized by the condensation of 2-amino-4-phenyl-1,3-thiazole with 8-formyl-7-hydroxy- 4-methylcoumarin. The probable structure of the complexes has been proposed on the basis of analytical and spectroscopic data (IR, UV-Vis, ESR, FAB-mass, and thermoanalytical). Electrochemical study of the complexes is also reported. Elemental analysis of the complexes confined them to stoichiometry of the type ML(2).2H(2)O [M = Co(II), Ni(II), and Cu(II)]. The Schiff base and its metal(II) complexes have been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Staphylococcus pyogenes, and Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, Aspergillus flavus, and Cladosporium) by the MIC method. The brine shrimp bioassay was carried out to study their in vitro cytotoxic properties, and also the Schiff base and its metal(II) complexes have been studied for DNA cleavage.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Study of Zn-Cu ferrite nanoparticles for LPG sensing.

    PubMed

    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)Cu(x)Fe2O4 (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.

  20. Thermodynamic Properties of Compressed CuX (X = Cl, Br) Compounds: Ab Initio Study

    NASA Astrophysics Data System (ADS)

    Bioud, Nadhira; Kassali, Kamel; Bouarissa, Nadir

    2017-04-01

    A pseudopotential plane wave method based on the density functional theory has been employed to study some thermodynamic properties of copper chloride (CuCl) and copper bromide (CuBr) compounds under the effect of temperature and pressure. The phase transition pressure, the unit cell volume, the isothermal bulk modulus, the constant volume heat capacity, the entropy, the Debye temperature, the Grüneisen parameter and the volumetric thermal expansion coefficient are studied in the pressure range 0-10 GPa, and for temperatures ranging from 0 K up to 650 K and 750 K for CuCl and CuBr, respectively. The phase transition pressure is found to be around 7.8 and 6.95 GPa for CuCI and CuBr, respectively. These values are respectively in reasonably good agreement with the experimental ones of 8.2 GPa and 6.8 GPa reported in the literature. Moreover, at room temperature and zero pressure, the heat capacity at constant volume and the Grüneisen parameter of both compounds of interest are found to be in good agreement with the available experimental and theoretical data. The information gathered from the present investigation may be useful for the study of the behavior of the fundamental properties of CuCI and CuBr under the influence of high temperature and pressure.

  1. An electrochemical and multispectroscopic study of corrosion of Ag-Pd-Cu-Au alloys.

    PubMed

    Niemi, L; Minni, E; Ivaska, A

    1986-06-01

    Corrosion of a multi-phase Ag-Pd-Cu-Au-based commercial dental casting alloy and a Cu-Pd-rich and Ag-rich single-phase alloy was studied by open-circuit potential measurements, atomic absorption spectrometry, and electron spectroscopy. The alloys were immersed in an artificial saliva solution for 24 hr while the open-circuit potentials of the alloys were measured. The potentials were found to stabilize at certain levels after a steep rise during the first hours of the experiment. Cu was found to dissolve considerably from the Cu-Pd-rich alloy, with simultaneous enrichment of Pd in the surface layer of the alloy. Ag dissolved slightly from the Ag-rich alloy, but both Cu and Ag were found to dissolve from the multi-phase alloy. Neither Pd nor Au dissolved from any of the alloys studied.

  2. Reactivity at the Cu2O(100):Cu-H2O interface: a combined DFT and PES study.

    PubMed

    Stenlid, J H; Soldemo, M; Johansson, A J; Leygraf, C; Göthelid, M; Weissenrieder, J; Brinck, T

    2016-11-09

    The water-cuprite interface plays an important role in dictating surface related properties. This not only applies to the oxide, but also to metallic copper, which is covered by an oxide film under typical operational conditions. In order to extend the currently scarce knowledge of the details of the water-oxide interplay, water interactions and reactions on a common Cu2O(100):Cu surface have been studied using high-resolution photoelectron spectroscopy (PES) as well as Hubbard U and dispersion corrected density functional theory (PBE-D3+U) calculations up to a bilayer water coverage. The PBE-D3+U results are compared with PBE, PBE-D3 and hybrid HSE06-D3 calculation results. Both computational and experimental results support a thermodynamically favored, and H2O coverage independent, surface OH coverage of 0.25-0.5 ML, which is larger than the previously reported value. The computations indicate that the results are consistent also for ambient temperatures under wet/humid and oxygen lean conditions. In addition, both DFT and PES results indicate that the initial (3,0;1,1) surface reconstruction is lifted upon water adsorption to form an unreconstructed (1 × 1) Cu2O(100) structure.

  3. 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.

  4. 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.

  5. Mechanism in the reaction of cytochrome c oxidase with organic hydroperoxides: an ESR spin-trapping investigation.

    PubMed

    Chen, Yeong-Renn; Mason, Ronald P

    2002-07-15

    Organic hydroperoxides are of great utility in probing the reaction mechanism and the toxicological consequences of lipid peroxidation. In the present study, ESR spin-trapping was employed to investigate the peroxidation of mitochondrial cytochrome c oxidase (CcO) with t-butyl hydroperoxide (t-BuOOH) and cumene hydroperoxide (CumOOH). The spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) was used to detect the radical species formed from the reaction of CcO with t-BuOOH. The presence of t-BuOOH-derived alkoxyl radical (t-BuO*) as the primary radical indicates reductive scission of the O-O bond by CcO. The ESR signal of DMPO/*Ot-Bu can be partially abolished by cyanide, implying that the reductive cleavage involved the haem a(3)Cu(B) binuclear site of CcO. A nitroso spin trap, 2-methyl-2-nitrosopropane (MNP), was used to detect and identify radical species from the reaction of CcO with CumOOH. In addition to the t-BuOOH-derived methyl, hydroxylmethyl and tertiary carbon-centred radicals, a protein-derived radical was detected. The intensity of the ESR signal from the protein radical increased with the CumOOH concentration at low CumOOH/CcO ratios, with maximal intensity at a ratio of 100 mol of CumOOH/mol of CcO. The immobilized protein radical adduct of MNP was stable and persistent after dialysis; it was also resistant to proteolytic digestion, suggesting that it was formed in the transmembrane region, a region that is not accessible to proteases. Its signal was greatly enhanced when CcO cysteine residues were chemically modified by N-ethylmaleimide, when the tryptophan residues in CcO were oxidized by N-bromosuccimide, and when tyrosine residues on the surface of CcO were iodinated, showing that a radical equilibrium was established among the cysteine, tryptophan and tyrosine residues of the protein-centred radical. Pre-treatment of CcO with cyanide prevented detectable MNP adduct formation, confirming that the haem a(3)-Cu(B) binuclear centre was the initial

  6. Na(I)/Cu(I-II) heterometallic cages interconnected by unusual linear 2-coordinate OCN-Cu(I)-NCO links: synthesis, structural, magnetostructural correlation and computational studies.

    PubMed

    Ray, Aurkie; Rosair, Georgina M; Rajeev, Ramanan; Sunoj, Raghavan B; Rentschler, Eva; Mitra, Samiran

    2009-11-21

    A new Na(I)/Cu(I-II) heterometallic coordination complex [Cu(2)L(2)Na(NCO)(2)Cu](n) (1) with an unusual architecture has been synthesised. In 1 cyclic Na-O-Cu-O-Cu cages constructed by the tetradentate N(2)O(2) donor Schiff base ligand (H(2)L = N,N'-bis(2-hydroxyacetophenone)propylenediimine) are interconnected to each other by a rare singly end-to-end bridged OCN-Cu(I)-NCO link generating 1D chain. The complex has been characterised by elemental, spectral and structural analysis. The cyclic voltammogram of 1 has been compared with the analogous complexes. Cryomagnetic susceptibility studies indicate the copper(II) centers in the cyclic Na-O-Cu-O-Cu cages are antiferromagnetically coupled with J = -13.8 cm(-1). Complex 1 is a new addition to a class of rare singly end-to-end cyanato bridged copper(I) species and interestingly the copper ions involved in OCN-Cu(I)-NCO links possess a linear 2-coordinate geometry. Density functional theory calculations have been carried out to gain additional insights into the metal and ligand orbitals participating in this unusual structure.

  7. Temperature effects on sex determination and ontogenetic gene expression of the aromatases cyp19a and cyp19b, and the estrogen receptors esr1 and esr2 in atlantic halibut (Hippoglossus hippoglossus).

    PubMed

    van Nes, Solveig; Andersen, Øivind

    2006-12-01

    The aromatase (CYP19) and estrogen receptor (ESR) play important roles in the molecular mechanism of sex determination and differentiation of lower vertebrates. Several studies have proven these mechanisms to be temperature sensitive, which can influence the direction of phenotypic gender development. A temperature study was conducted to examine the effect of temperature on the sex differentiation in farmed Atlantic halibut. Sexually undifferentiated larvae were exposed to 7 degrees C, 10 degrees C, or 13 degrees C during gonadal differentiation. Temperature effects on the transcription rate of the aromatase genes cyp19a (ovary type) and cyp19b (brain type) and the ESR genes esr1 and esr2 were examined by quantitative real-time PCR. With increasing temperatures, both cyp19a mRNA levels and the female incidence showed a decreasing trend, thus strongly indicating a relation between the expression of cyp19a and morphological ovary differentiation. In contrast to cyp19a, the levels of cyp19b, esr1, and esr2 mRNA strongly increased in all temperature groups throughout the study period, and did not show obvious temperature-related expression patterns. The present data provide evidence that posthatching temperature exposure significantly affects the expression of cyp19a mRNA during the developmental period and that high temperature possibly influences genetic sex determination in Atlantic halibut. Though, the female incidence never exceeded 50%, suggesting that only the homogametic (XX) female is thermolabile. So whereas temperature treatment is not likely suitable for direct feminization in halibut, the possibility for high-temperature production of XX neomales for broodstock to obtain all-female offspring by crossing with XX females is suggested.

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. Cu-Ni core-shell nanoparticles: structure, stability, electronic, and magnetic properties: a spin-polarized density functional study

    NASA Astrophysics Data System (ADS)

    Wang, Qiang; Wang, Xinyan; Liu, Jianlan; Yang, Yanhui

    2017-02-01

    Bimetallic core-shell nanoparticles (CSNPs) have attracted great interest not only because of their superior stability, selectivity, and catalytic activity but also due to their tunable properties achieved by changing the morphology, sequence, and sizes of both core and shell. In this study, the structure, stability, charge transfer, electronic, and magnetic properties of 13-atom and 55-atom Cu and Cu-Ni CSNPs were investigated using the density functional theory (DFT) calculations. The results show that Ni@Cu CSNPs with a Cu surface shell are more energetically favorable than Cu@Ni CSNPs with a Ni surface shell. Interestingly, three-shell Ni@Cu12@Ni42 is more stable than two-shell Cu13@Ni42, while two-shell Ni13@Cu42 is more stable than three-shell Cu@Ni12@Cu42. Analysis of Bader charge illustrates that the charge transfer increases from Cu core to Ni shell in Cu@Ni NPs, while it decreases from Ni core to Cu shell in Ni@Cu NPs. Furthermore, the charge transfer results that d-band states have larger shift toward the Fermi level for the Ni@Cu CSNPs with Cu surface shell, while the Cu@Ni CSNPs with Ni surface shell have similar d-band state curves and d-band centers with the monometallic Ni NPs. In addition, the Cu-Ni CSNPs possess higher magnetic moment when the Ni atoms aggregated at core region of CSNPs, while having lower magnetic moment when the Ni atoms segregate on surface region. The change of the Cu atom location in CSNPs has a weak effect on the total magnetic moment. Our findings provide useful insights for the design of bimetallic core-shell catalysts.

  15. Atom probe study of Cu-poor to Cu-rich transition during Cu(In,Ga)Se{sub 2} growth

    SciTech Connect

    Couzinie-Devy, F.; Cadel, E.; Pareige, P.; Barreau, N.; Arzel, L.

    2011-12-05

    Atomic scale chemistry of polycrystalline Cu(In,Ga)Se{sub 2} (CIGSe) thin film has been characterized at key points of the 3-stage process using atom probe tomography. 3D atom distributions have been reconstructed when the layer is Cu-poor ([Cu]/([Ga] + [In]) < 1), Cu-rich ([Cu]/([Ga] + [In]) > 1), and at the end of the process. Particular attention has been devoted to grain boundary composition and Na atomic distribution within the CIGSe layer. Significant variation of composition is highlighted during the growing process, providing fundamental information helping the understanding of high efficiency CIGSe formation.

  16. Studies on the thermoluminescence spectra and thermal stability of LiF:Mg,Cu, LiF:Mg,Cu,Na and LiF:Mg,Cu,Si

    NASA Astrophysics Data System (ADS)

    Yang, B.; Lu, Q.; Wang, S.; Townsend, P. D.

    2005-09-01

    Four thermoluminescence (TL) peaks at 60-90, 100-130, 130-180 and 180-220 °C (the main peak) were observed from LiF:Mg,Cu, LiF:Mg,Cu,Na and LiF:Mg,Cu,Si. The recorded emission bands were at 375 and 414 nm in LiF:Mg,Cu, at 379 and 424 nm in LiF:Mg,Cu,Na and 378 and 425 nm in LiF:Mg,Cu,Si. The loss of TL intensity and temperature shift of the main peak were observed in LiF:Mg,Cu, LiF:Mg,Cu,Na, LiF:Mg,Cu,Si, LiF:Mg,Cu,Na,Si and LiF:Mg as well as in LiF:Mg,Cu,P, when the sample was heated to above 270 °C. It is suggested that those are the common behaviors in the Mg doped LiF samples, if the concentration of magnesium is properly high. Those behaviors are supposed to be associated with the precipitated phase of Mg and the secondary phase - Mg/(other impurities) complex.

  17. 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.

  18. 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.

  19. 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).

  20. 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.

  1. Generating Cu(II)-Oxyl / Cu(III)-Oxo Species from Cu(I)-α-Ketocarboxylate Complexes and O2: In silico Studies on Ligand Effects and C-H-activation Reactivity

    PubMed Central

    Huber, Stefan M.; Ertem, M. Zahid; Aquilante, Francesco

    2010-01-01

    A mechanism for the oxygenation of Cu(I) complexes with α-ketocarboxylate ligands is elaborated that is based on a combination of density functional theory and multireference second-order perturbation theory (CASSCF/CASPT2) calculations. The reaction proceeds in a manner largely analogous to those of similar Fe(II) α-ketocarboxylate systems, i.e. by initial attack of a coordinated oxygen molecule on a ketocarboxylate ligand with concomitant decarboxylation. Subsequently, two reactive intermediates may be generated, a Cu-peracid structure and a [CuO]+ species, both of which are capable of oxidizing a phenyl ring that is a component of the supporting ligand. Hydroxylation by the [CuO]+ species is predicted to proceed with a smaller activation free energy. The effects of electronic and steric variatons on the oxygenation mechanisms were studied by introducing substituents at several positions of the ligand backbone and by investigating various N-donor ligands. In general, more electron-donation by the N-donor ligand leads to increased stabilization of the more Cu(II)/Cu(III)-like intermediates (oxygen adducts and [CuO]+ species) relative to the more Cu(I)-like peracid intermediate. For all ligands investi-gated, the [CuO]+ intermediates are best described as Cu(II)-O•- species having triplet ground states. The reactivity of these compounds in C-H abstraction reactions decreases with more electron-donating N-donor ligands, which also increase the Cu-O bond strength, although the Cu-O bond is generally predicted to be rather weak (with a bond order of about 0.5). A comparison of several methods to obtain singlet energies for the reaction intermediates indicates that multireference second-order perturbation theory is likely more accurate for the initial oxygen adducts, but not necessarily for subsequent reaction intermediates. PMID:19322769

  2. 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.

  3. Synthesis, spectral and thermal studies of Co(II), Ni(II) and Cu(II) complexes 1-(4,6-dimethyl-pyrimidin-2-ylazo)-naphthalen-2-ol.

    PubMed

    Gaber, M; Ayad, M M; El-Sayed, Y S Y

    2005-11-01

    The electronic absorption spectra of 1-(4,6-dimethyl-pyrimidin-2-ylazo)-naphthalen-2-ol is studied in organic solvents of different polarity as well as in buffer solutions of varying pH values at different temperatures and different ratios of methanol. The probable structure of the azodye has been assigned on the basis of spectral studies (IR and (1)H NMR). The effect of Co(II), Ni(II) and Cu(II) ions on the emission spectrum of the free azodye is also assigned. The stoichiometry of the metal complexes is determined spectrophotometrically and conductometrically. Novel complexes of Co(II), Ni(II) and Cu(II) with the pyrimidine azodye have been synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic as well as ESR spectral studies The thermal decomposition of the metal complexes is studied by TGA and DTA techniques. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation are estimated.

  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. 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.

  7. 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.

  8. Application of ESR spin label oximetry in food science.

    PubMed

    Zhou, Yu-Ting; Yin, Jun-Jie; Lo, Y Martin

    2011-12-01

    Lipid oxidation attributed to the presence of oxygen has long been a focal area for food science research due in early years mainly to its broad impact on the quality and shelf stability. The need to effectively strategize interventions to detect and eventually eliminate lipid oxidation in food remains as evidence on nutritional and health implications continue to accumulate. Electron spin resonance (ESR) spin label oximetry has been shown capable of detecting dissolved oxygen concentration in both liquid and gaseous phases based on the collision between oxygen and stable free radicals. This review aimed to summarize not just the principles and rationale of ESR spin label oximetry but also the wide spectrum of ESR spin label oximetry applications to date. The feasibility to identify in very early stage oxygen generation and consumption offers a promising tool for controlling lipid oxidation in food and biological systems.

  9. Cu(I)-N heterocyclic carbene complexes: Synthesis, catalysis and DFT studies

    NASA Astrophysics Data System (ADS)

    Dinda, Joydev; Roymahapatra, Gourisankar; Sarkar, Deblina; Mondal, Tapan K.; Al-Deyab, Salem S.; Sinha, Chittaranjan; Hwang, Wen-Shu

    2017-01-01

    The structural, spectroscopic and catalytic properties of the two Cu(I) complexes [Cu2(L1)2](PF6)2;(1) and [Cu2(L2)2](PF6)2; (2), bearing proligands 2,6-bis-(N-methylimidazolium)pyrazine hexafluorophosphate (L1) and 2,6-bis-(N-methylbenzimidazolium)pyrazine hexafluorophosphate (L2), have been investigated. The solid state structure of 1 has been determined by X-ray diffraction studies, while DFT computation technique has been used to optimize structure 2. From molecular orbital calculations using TD-DFT, the absorption bands are assigned to metal to ligand charge transfer(MLCT) along with some inter ligand charge transfer (ILCT) transitions. Complexes 1 and 2 possess very weak Cu(I)sbnd Cu(I) interactions within the reported distance 2.947-3.020 Å. They are expected to have luminescent properties due to Cu(I)sbnd Cu(I) interactions. Preliminary studies revealed both complexes to possess catalytic efficiency in general hydrosilylation reactions.

  10. 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.

  11. 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.

  12. Study on multicaloric effect of CuO induced multiferroic

    NASA Astrophysics Data System (ADS)

    Kumar, Amit; Yadav, K. L.

    2014-08-01

    One of the induced multiferroic materials, CuO has the magnetic as well as ferroelectric phase transition at same temperature (TN1 ˜ 213 K, TC and TN2 ˜ 230 K). These type of materials can show two types of entropy; magnetic field induced entropy (Magnetocaloric Effect) as well as electeric field induced entropy (Electrocaloric Effect). The presence of both type of entropy may be called "Multicaloric Entropy" (M. Vopson, Solid State Commun. 152, 2067 (2012) and Meng et al., Phys. Lett. A 377, 567 (2013)). We observed that "Multicaloric Entropy" in the induced multiferroic materials also depends on the magnetoelectric interaction (γ). Therofore, this numerical attempt to calculate the entropy of CuO may be useful for the future "electro-magnetic" based refrigerator technology.

  13. Surface alloying of Pb on Cu(111): a TEAS study

    NASA Astrophysics Data System (ADS)

    de Beauvais, Ch.; Girard, Y.; Pérard, C.; Croset, B.; Mutaftschiev, B.

    1996-11-01

    Thermal energy atom scattering on vacuum deposited Pb submonolayers on Cu(111) in close to equilibrium conditions, at substrate temperatures between 303 K and 413 K, gives evidence for: (a) decoration by Pb atoms of monatomic steps on the Cu surface at degree of coverage 0 < θ < 0.004; (b) formation of disordered surface alloy in the first lattice plane of the copper substrate in the coverage range 0.004 < θ < 0.21; (c) formation of non-alloyed Pb layer with a p(4 × 4) structure above this coverage, up to the monolayer ( θ ≈ 0.56). The latter transition is shown to be of first order. The role of the deposition kinetics in far from equilibrium conditions is pointed out.

  14. Molecular Dynamics study of Pb overlayer on Cu(100)

    NASA Technical Reports Server (NTRS)

    Karimi, M.; Tibbits, P.; Ila, D.; Dalins, I.; Vidali, G.

    1991-01-01

    Isothermal-isobaric Molecular Dynamics (MD) simulation of a submonolayer Pb film in c(2x2) ordered structure adsorbed on a Cu(100) substrate showed retention of order to high T. The Embedded Atom Method (EAM) calculated the energy of atoms of overlayer and substrate. The time-averaged squared modulus of the two dimensional structure factor for the Pb overlayer measured the order of the overlayer. The results are for increasing T only, and require verification by simulated cooling.

  15. Synthesis, characterization and ESR studies of powder Zn0.95-xMg0.05AlxO (x=0, 0.01, 0.02, 0.05, and 0.1) nanocrystals

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    Zn0.95-xMg0.05AlxO solutions with different (x=0.0, 0.01, 0.02, 0.05, and 0.1) compositions were synthesized by the sol-gel technique using Zn, Mg and Al based alkoxide. The effects of doping ratio and annealing temperature on the structure and magnetic properties were investigated systematically. The phase and the crystal structure of the Zn0.95-xMg0.05AlxO nanoparticles were characterized using X-Ray diffraction. The size and microstructure of samples were characterized by Scanning Electron Microscope and X-Ray diffraction. The particle sizes of nanoparticles were observed in the 20-25 nm range. ESR spectra of Zn0.95-xMg0.05AlxO powder samples were collected at room temperature on a Bruker EMX model X-band spectrometer operating at a frequency of 9.50 GHz.

  16. 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.

  17. 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).

  18. Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios.

    PubMed

    Giordanino, Filippo; Vennestrøm, Peter N R; Lundegaard, Lars F; Stappen, Frederick N; Mossin, Susanne; Beato, Pablo; Bordiga, Silvia; Lamberti, Carlo

    2013-09-21

    Cu-SSZ-13 has been characterized by different spectroscopic techniques and compared with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios and prepared by the same ion exchange procedure. On vacuum activated samples, low temperature FTIR spectroscopy allowed us to appreciate a high concentration of reduced copper centres, i.e. isolated Cu(+) ions located in different environments, able to form Cu(+)(N2), Cu(+)(CO)n (n = 1, 2, 3), and Cu(+)(NO)n (n = 1, 2) upon interaction with N2, CO and NO probe molecules, respectively. Low temperature FTIR, DRUV-Vis and EPR analysis on O2 activated samples revealed the presence of different Cu(2+) species. New data and discussion are devoted to (i) [Cu-OH](+) species likely balanced by one framework Al atom; (ii) mono(μ-oxo)dicopper [Cu2(μ-O)](2+) dimers observed in Cu-ZSM-5 and Cu-β, but not in Cu-SSZ-13. UV-Vis-NIR spectra of O2 activated samples reveal an intense and finely structured d-d quadruplet, unique to Cu-SSZ-13, which is persistent under SCR conditions. This differs from the 22,700 cm(-1) band of the mono(μ-oxo)dicopper species of the O2 activated Cu-ZSM-5, which disappears under SCR conditions. The EPR signal intensity sets Cu-β apart from the others.

  19. Degradation and rejuvenation studies of AC electroluminescent ZnS:Cu,Cl phosphors

    NASA Astrophysics Data System (ADS)

    Stanley, Jacob; Jiang, Yu; Bridges, Frank; Carter, Sue A.; Ruhlen, Laurel

    2010-02-01

    We report detailed degradation and rejuvenation studies of AC electroluminescence (EL) of the phosphor ZnS:Cu,Cl, aiming to better understand the physical mechanisms that control EL emission. We find that the AC EL emission spectra vary considerably with the AC driving frequency but all spectra can be fit to a sum of four Gaussians. During degradation, although there is a large overall decrease in amplitude, the shape of the emission spectra measured at a given AC frequency does not change. Annealing the samples after they are significantly degraded can rejuvenate the phosphors with a maximum rejuvenation occurring (for fixed annealing times) near 180 °C. Further, these test cells can be degraded and rejuvenated multiple times. However studies at slightly higher annealing temperatures (240 °C) show significant thermal degradation and, perhaps more importantly, a change in the spectral shape; this likely indicates that two distinct mechanisms are then operative. In extended x-ray absorption fine structure (EXAFS) experiments we find that the CuS nanoprecipitates in the ZnS host (~75% of the Cu is in the CuS precipitates) do not change significantly after the 240 °C anneal; these experiments also provide a more detailed comparison of the local structure about Cu in pure CuS, and in ZnS:Cu,Cl. In addition, the EXAFS experiments also place an upper limit on the fraction of possible interstitial Cu sites, proposed as a blue emission center, at less than 10%. The combined experiments place strong constraints on the mechanisms for degradation and rejuvenation and suggest that EL degradation is most likely caused by either Cu or Cl diffusion under high E-fields, while thermal diffusion at slightly elevated temperatures without E-fields present, re-randomizes the (isolated) dopant distributions. Higher T anneals appear to damage the sharp tips on the precipitates.

  20. ESR measurements of phosphorus dimers in isotopically enriched 28Si silicon

    NASA Astrophysics Data System (ADS)

    Shankar, S.; Tyryshkin, A. M.; Lyon, S. A.

    2015-06-01

    Dopants in silicon have been studied for many decades using optical and electron spin resonance (ESR) spectroscopy. Recently, new features have been observed in the spectra of dopants in isotopically enriched 28Si since the reduced inhomogeneous linewidth in this material improves spectral resolution. With this in mind, we measured ESR on exchange coupled phosphorus dimers in 28Si and report two results. First, a fine structure is observed in the ESR spectrum arising from state mixing by the hyperfine coupling to the 31P nuclei, which is enhanced when the exchange energy is comparable to the Zeeman energy. This fine structure enables us to spectroscopically address two separate dimer subensembles, the first with exchange (J ) coupling ranging from 2 to 7 GHz and the second with J ranging from 6 to 60 GHz. Next, the average spin relaxation times T1 and T2 of both dimer subensembles were measured using pulsed ESR at 0.35 T. Both T1 and T2 for transitions between triplet states of the dimers were found to be identical to the relaxation times of isolated phosphorus donors in 28Si, with T2=4 ms at 1.7 K limited by spectral diffusion due to dipolar interactions with neighboring donor electron spins. This result, consistent with theoretical predictions, implies that an exchange coupling of 2-60 GHz does not limit the dimer T1 and T2 in bulk Si at the 10-ms time scale.

  1. NiFe/CoFe/Cu/CoFe/MnIr spin valves studied by ferromagnetic resonance

    NASA Astrophysics Data System (ADS)

    Timopheev, A. A.; Sobolev, N. A.; Pogorelov, Y. G.; Bunyaev, S. A.; Teixeira, J. M.; Cardoso, S.; Freitas, P. P.; Kakazei, G. N.

    2013-05-01

    Ion-beam deposited (Glass/Ta/NiFe/CoFe/Cu/CoFe/MnIr/Ta) spin valves (SVs) with a Cu-spacer thickness (tCu) varying from 14 to 28 Å have been studied by ferromagnetic resonance (FMR) and magnetoresistance (MR) measurements. With respect to the interlayer coupling strength between the free and fixed ferromagnetic layers, the samples have been divided in those with a weak coupling (for tCu > 16 Å) and a strong coupling regimes (for tCu ≤ 16 Å). The FMR behavior in these two regimes is quite different. For the weakly coupled series, there are two well-defined FMR peaks stemming from the free and fixed layers. Their in-plane angular dependences exhibit 180° and 360° symmetries, respectively. For the strongly coupled SVs, the resonance modes are hybridized and possess features of both layers simultaneously. The main coupling mechanism between the two layers, as concluded from the FMR and MR measurements, is the Néel "orange-peel" magnetostatic interaction, accompanied by a direct exchange due to pinholes in the Cu spacer for tCu < 17 Å.

  2. EPR, magnetization, and resistivity studies in doped (4-f or 3-d ions) and undoped RBa2Cu3Oy high TC superconductors (R=Y,Pr,Nd,Eu,Gd,Ho,Er, or Yb) (abstract)

    NASA Astrophysics Data System (ADS)

    Vier, D. C.; Smyth, J. F.; Salling, C. T.; Schultz, S.; Dalichaouch, Y.; Lee, B. W.; Yang, K. N.; Torikachvili, M.; Maple, M. B.; Oseroff, S. B.; Fisk, Z.; Thompson, J. D.; Smith, J. L.; Zirngiebl, E.

    1988-04-01

    We have measured electron paramagnetic resonance (EPR), resistivity, and dc susceptibility from 2 to 300 K for the oxide high Tc superconductors (R)Ba2Cu3Oy (R=Y,Pr,Nd,Eu,Gd,Ho,Er,Tm, or Yb). Selected systems were doped with 3-d ions (Cr,Mn,Fe,Ni,Co, or Zn) or 4-f ions (Gd or Er) which presumably substitute for the Cu or R site, respectively. In the systems studied we have observed an EPR line at low temperatures (T<40 K), which exhibits an increase in intensity and decrease in field for resonance as the temperature is lowered. The ESR linewidth is also temperature dependent and exhibits a minimum at about 15 K. An additional EPR line that can be associated with a Gd3+, Mn2+ or Er3+ ion was observed for those samples where these ions were present as dilute impurities. In some of the samples another EPR signal is observed with properties that depend on sample preparation conditions. The behavior and origin of all lines will be discussed. The variation of Tc with concentration of the added impurities over the range (1%-15%) will also be presented, and compared with previous studies in other superconducting systems.

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

    DOE PAGES

    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

  4. 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.

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

    DOE PAGES

    Yang, Ji -Hui; Yin, Wan -Jian; Park, Ji -Sang; ...

    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

  6. 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.

  7. 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.

  8. An EPR and optical absorption study of Cu(2+) doped in disodium malonate trihydrate single crystal.

    PubMed

    Yarbaşi, Zeynep; Karabulut, Bünyamin; Karabulut, Abdulhalik

    2009-03-01

    Single crystals and powder electron paramagnetic resonance (EPR) studies of Cu(2+)-doped disodium malonate trihydrate [C(3)H(2)O(4)Na(2).3H(2)O] have been carried out at room temperature. The angular variation of the disodium malonate trihydrate single crystal have shown that two different Cu(2+) complexes are located in different chemical environments, and each environment contains one magnetically inequivalent Cu(2+) sites in distinct orientations occupying substitutional positions in the lattice and show very high angular dependence. The principal values of the g and the hyperfine tensors were determined and were found to be in agreement with the literature values. Crystal field around the Cu(2+) ion is nearly rhombic. The optical absorption studies show two bands at 603nm (16584cm(-1)) and 890nm (11236cm(-1)) which confirm the rhombic symmetry. The crystals field parameters and than the wave function are determined.

  9. An EPR and optical absorption study of Cu 2+ doped in disodium malonate trihydrate single crystal

    NASA Astrophysics Data System (ADS)

    Yarbaşı, Zeynep; Karabulut, Bünyamin; Karabulut, Abdulhalik

    2009-03-01

    Single crystals and powder electron paramagnetic resonance (EPR) studies of Cu 2+-doped disodium malonate trihydrate [C 3H 2O 4Na 2·3H 2O] have been carried out at room temperature. The angular variation of the disodium malonate trihydrate single crystal have shown that two different Cu 2+ complexes are located in different chemical environments, and each environment contains one magnetically inequivalent Cu 2+ sites in distinct orientations occupying substitutional positions in the lattice and show very high angular dependence. The principal values of the g and the hyperfine tensors were determined and were found to be in agreement with the literature values. Crystal field around the Cu 2+ ion is nearly rhombic. The optical absorption studies show two bands at 603 nm (16584 cm -1) and 890 nm (11236 cm -1) which confirm the rhombic symmetry. The crystals field parameters and than the wave function are determined.

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

    SciTech Connect

    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 will prefer to stay at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.

  11. 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.

  12. 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.

  13. 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.

  14. EPR Studies of Cu2+ in dl-Aspartic Acid Single Crystals

    NASA Astrophysics Data System (ADS)

    Karabulut, B.; Tapramaz, R.; Bulut, A.

    1999-04-01

    EPR studies of Cu2+ doped dl-Aspartic Acid [NH2CH(CH2COOH)COO] powder and single crystal have been carried out at 113 and 300 K. The principal hyperfine and g values, covalancy parameter, mixing coefficients and Fermi-contact term of the complex were obtained, and the ground-state wavefuntion of the Cu2+ ion in the lattice has been constructed.

  15. Solvothermal growth and morphology study of Cu 2Se films

    NASA Astrophysics Data System (ADS)

    Lin, Fei; Bian, Guo-Qing; Lei, Zhi-Xin; Lu, Zhe-Jun; Dai, Jie

    2009-05-01

    Solvothermal growth of cuprous selenide films on copper substrate has been succeeded by treating copper foil in the mixture of selenium powder and amines or hydrazine. The films were characterized by methods of XRD, SEM, TEM and optical spectra (Cu 2Se, JCPDS 47-1448). Films with hexagonal microcrystals can be obtained in hydrazine/water reaction system. When CTAB (CTAB = cetyltrimethylammonium bromide) is added to the system, the film is composed of thin leaf-like microcrystals. When ethylenediamine (en) is used as solvent, the leaf-like microcrystals are crimped.

  16. Theory of two-dimensional ESR with nuclear modulation

    NASA Astrophysics Data System (ADS)

    Gamliel, Dan; Freed, Jack H.

    A formalism for computing 2D ESR lineshapes with nuclear modulation is developed in a form which is useful for planning phase cycles for particular purposes. A simple method of processing spectra, utilizing quadrature detection, is shown to enhance the selectivity of the phase cycling techniques. Computed ESR-COSY, ESR-SECSY, and 2D ELDOR lineshapes are presented for several kinds of polycrystalline and single-crystal samples which exhibit nuclear modulation, due to one or several nuclei. The two-dimensional methods are found to give more detailed structural information than the corresponding ESEEM spectra. New phase cycles are found to eliminate completely all transverse and axial peaks in 2D ELDOR and in ESR-COSY, and at the same time eliminate all artifacts arising from incomplete image rejection. Other phase cycles are presented for selecting in those experiments only axial peaks, for measuring T1. It is also shown how selective phase cycles may help to distinguish between coherent and exchange cross peaks. In the special case of nitroxides in typical Zeeman fields, there are no significant nuclear modulation effects from the 14N nuclear spin interaction, but those from the protons (or deuterons) will, in general, be significant.

  17. Effect of annealing on Cu precipitates in H ion irradiated Fe-0.6%Cu studied by positron annihilation

    NASA Astrophysics Data System (ADS)

    Jin, Shuoxue; Zhang, Peng; Lu, Eryang; Wang, Baoyi; Yuan, Daqing; Wei, Long; Cao, Xingzhong

    2016-10-01

    Fe-0.6%Cu alloy was irradiated with H ions to 0.1 dpa, and then annealed for 30 min from 150 °C to 500 °C. We focused the evolution of Cu precipitates in irradiated Fe-0.6%Cu alloy after the isochronal annealing from the perspective of positron annihilation. The ΔW parameters after thermal annealing (400 °C and 500 °C) were much larger than that induced by 0.1 dpa H irradiation. Annealing could promote the aggregation of the Cu-vacancy complexes, and form the Cu cluster-vacancies complexes. When the vacancy-like defects recovered around 500 °C, it meant the formation and growing of the defect-free Cu precipitates.

  18. 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.

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

    SciTech Connect

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

    2016-01-28

    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.

  20. 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.

  1. 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.

  2. ESR1 inhibits hCG-induced steroidogenesis and proliferation of progenitor Leydig cells in mice

    PubMed Central

    Oh, Yeong Seok; Koh, Il Kyoo; Choi, Bomi; Gye, Myung Chan

    2017-01-01

    Oestrogen is an important regulator in reproduction. To understand the role of oestrogen receptor 1 (ESR1) in Leydig cells, we investigated the expression of ESR1 in mouse Leydig cells during postnatal development and the effects of oestrogen on steroidogenesis and proliferation of progenitor Leydig cells (PLCs). In Leydig cells, the ESR1 expression was low at birth, increased until postnatal day 14 at which PLCs were predominant, and then decreased until adulthood. In foetal Leydig cells, ESR1 immunoreactivity increased from birth to postnatal day 14. These suggest that ESR1 is a potential biomarker of Leydig cell development. In PLCs, 17β-estradiol and the ESR1-selective agonist propylpyrazoletriol suppressed human chorionic gonadotropin (hCG)-induced progesterone production and steroidogenic gene expression. The ESR2-selective agonist diarylpropionitrile did not affect steroidogenesis. In PLCs from Esr1 knockout mice, hCG-stimulated steroidogenesis was not suppressed by 17β-estradiol, suggesting that oestrogen inhibits PLC steroidogenesis via ESR1. 17β-estradiol, propylpyrazoletriol, and diarylpropionitrile decreased bromodeoxyuridine uptake in PLCs in the neonatal mice. In cultured PLCs, 17β-estradiol, propylpyrazoletriol, and diarylpropionitrile reduced hCG-stimulated Ki67 and Pcna mRNA expression and the number of KI67-positive PLCs, suggesting that oestrogen inhibits PLC proliferation via both ESR1 and ESR2. In PLCs, ESR1 mediates the oestrogen-induced negative regulation of steroidogenesis and proliferation. PMID:28266530

  3. Thermally stimulated luminescence studies of undoped, Cu- and Mn-doped CaSO4 compounds

    NASA Astrophysics Data System (ADS)

    Manam, J.; Das, S.

    Thermally stimulated luminescence (TSL) of undoped and doped CaSO4 with activators such as Cu and Mn has been investigated. The polycrystalline samples of undoped and doped CaSO4 are prepared by the melting method. The formation of CaSO4 compound is confirmed by X-ray diffraction and Fourier transform infrared studies. Scanning electron microscopic studies of CaSO4 are also carried out. The TSL glow curves of undoped CaSO4, Cu- and Mn-doped CaSO4 are studied. Comparison of the thermoluminescence (TL) intensity of the most intensive glow peak of Cu-doped CaSO4 compound with that of undoped CaSO4 shows that addition of Cu impurity in CaSO4 compound enhances the TL intensity by about four times. However, the addition of Mn impurity to undoped CaSO4 increases the TL intensity by about three times when compared with that of undoped CaSO4. The TL-dose dependence of all three samples was studied and was observed to be almost linear in the studied range of irradiation time. Among the samples studied, namely undoped CaSO4 and Cu- and Mn-doped CaSO4, Cu-doped CaSO4 is found to be the most sensitive. The trap parameters, namely order of kinetics (b), activation energy (E) and frequency factor (s) associated with the most intensive glow peaks of CaSO4:Mn, CaSO4:Cu and CaSO4 phosphors were determined using the glow curve shape (Chen's) method.

  4. Experimental and molecular dynamics studies in copper electro chemical mechanical polishing (Cu-ECMP)

    NASA Astrophysics Data System (ADS)

    Kandasamy Arulmozhi, Anant

    In recent times, copper electrochemical mechanical polishing (Cu ECMP) has received a great deal of interest from electrochemists and the semiconductor manufacturing industry. This attention is primarily due to its potential for yielding relatively defect-free surfaces with improved surface integrity compared to chemical mechanical planarization (CMP). In this work, Cu ECMP apparatus integrated with a sensing and data acquisition system was developed to polish phi4 inch (phi100 mm) blank Cu wafer surfaces to a finish of Ra< 15nm, and continuously gather voltage and current signals during Cu ECMP process at a sampling rate of 100Hz. Experimental studies were carried out to understand the effects of anodic voltage, pH, and pad pressure on the material removal rate (MRR) and surface roughness (Ra). Understanding the process from an atomistic standpoint helps us gain better control over the process and aids us in optimizing the key process output variables (KPOV). In order to gain a better understanding of the process, the molecular dynamic simulation (MDS) technique was adopted to develop a model to depict the real-time formation of copper (II) hexa-hydrate molecule Cu[(H2O)6] 2+, which is one of the key elements of the passivation layer formed over the Cu surface during ECMP. The behavior of the complex molecule under an electric force field was simulated to observe the process from a molecular perspective. From the trajectory of Cu2+, it was found that the velocity of copper ion increased with increase in applied voltage. Furthermore, the current carried by a single Cu2+ ion was computed based on the applied voltage and velocity of the ion.

  5. Study of the mechanisms of Cu2+ biosorption by ethanol/caustic-pretreated baker's yeast biomass.

    PubMed

    Zhang, Yunsong; Liu, Weiguo; Xu, Meng; Zheng, Fei; Zhao, Maojun

    2010-06-15

    Baker's yeast biomass was pretreated by ethanol and caustic soda, and then the pristine baker's yeast, ethanol pretreated baker's yeast (ethanol-baker's yeast) and caustic soda pretreated baker's yeast (caustic-baker's yeast) were utilized as biosorbents to adsorb Cu(2+) in aqueous solution. The influence of different parameters on Cu(2+) uptake by the three biomasses, such as initial Cu(2+) concentration, initial pH of solution, contact time and temperature, was studied. The mechanism of Cu(2+) binding by biomass was investigated by a number of techniques. Evidence from potentiometric titration revealed that the concentration of carboxyl and amino groups is higher on the caustic and ethanol-baker's yeast compared to the pristine baker's yeast and FTIR spectra confirmed carboxyl, and amino groups on the surface of baker's yeast could be available for characteristic coordination bonding with Cu(2+). In addition, SEM and Zeta potential of the three samples show that caustic and ethanol-pretreatment resulted in the change of baker's yeast surface structure and charge which is relative to adsorption. These results demonstrate that the increase of biosorption capacity for Cu(2+) by ethanol and caustic-baker's yeast was attributed to the increase and exposure of carboxyl and amino groups on the surface of biomass sample.

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

    DOE PAGES

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

    2016-04-09

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

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

    SciTech Connect

    Chen, Youxing; Li, Nan; Bufford, Daniel Charles; Li, Jin; Hattar, Khalid Mikhiel; Wang, Haiyan; Zhang, Xinghang

    2016-04-09

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

  8. X-ray emission study of ion beam mixed Cu/Al films on polyimide

    SciTech Connect

    Kurmaev, E.Z.; Zatsepin, D.A.; Winarski, R.P.; Stadler, S.; Ederer, D.L.; Moewes, A.; Fedorenko, V.V.; Shamin, S.N.; Galakhov, V.R.; Chang, G.S.; Whang, C.N.

    1999-03-01

    Cu (40 nm)/Al/polyimide/Si was mixed with 80 keV Ar{sup +} and N{sub 2}{sup +} from 5.0{times}10{sup 15} to 15{times}10{sup 15} ions/cm{sup 2}. Ultrasoft x-ray emission valence spectra (XES) of Cu, C, N and O excited by electron and photon radiation were used for study of chemical reactions in Cu/Al/PI/Si and PI/Si systems induced by ion beam mixing in dependence of type of ions and dose. It is found that ion beam mixing changes the chemical state of Cu atoms with respect to that of pure metal. These changes depend on the dose of ion beam bombardment and type of ions and are attributed to a formation of CuAl{sub 2}O{sub 4} interfacial layer, which can be responsible for enhanced interfacial adhesion strength. On the other hand, it is shown that the shape of C {ital K}{alpha}, N {ital K}{alpha} and O {ital K}{alpha} XES of ion beam mixed polyimide layer (PI/Si) is modified with ion bombardment. This means that the ion-beam mixing process is able to break the bonding of constituent atoms of irradiated PI layers and can induce the formation of chemically bonded complexes linking atoms in the Cu, Al and PI layers.{copyright} {ital 1999 American Vacuum Society.}

  9. Structure and Gas-Phase Thermochemistry of a Pd/Cu Complex: Studies on a Model for Transmetalation Transition States.

    PubMed

    Oeschger, Raphael J; Chen, Peter

    2017-01-25

    A heterobimetallic Pd(II)/Cu(I) complex was prepared and characterized by X-ray diffraction analysis. The crystal structure shows a remarkably short Pd-Cu bond and a trigonal ipso carbon atom. The Pd-Cu interaction, as determined by energy-resolved collision-induced dissociation cross-section experiments, models the net stabilizing energy of the Pd-Cu interaction in the transition state of the transmetalation step in Pd/Cu-catalyzed cross-coupling reactions. The bonding situation in the bimetallic dinuclear complex has been studied by atoms-in-molecules analysis.

  10. Comparative reliability studies and analysis of Au, Pd-coated Cu and Pd-doped Cu wire in microelectronics packaging.

    PubMed

    Chong Leong, Gan; Uda, Hashim

    2013-01-01

    This paper compares and discusses the wearout reliability and analysis of Gold (Au), Palladium (Pd) coated Cu and Pd-doped Cu wires used in fineline Ball Grid Array (BGA) package. Intermetallic compound (IMC) thickness measurement has been carried out to estimate the coefficient of diffusion (Do) under various aging conditions of different bonding wires. Wire pull and ball bond shear strengths have been analyzed and we found smaller variation in Pd-doped Cu wire compared to Au and Pd-doped Cu wire. Au bonds were identified to have faster IMC formation, compared to slower IMC growth of Cu. The obtained weibull slope, β of three bonding wires are greater than 1.0 and belong to wearout reliability data point. Pd-doped Cu wire exhibits larger time-to-failure and cycles-to-failure in both wearout reliability tests in Highly Accelerated Temperature and Humidity (HAST) and Temperature Cycling (TC) tests. This proves Pd-doped Cu wire has a greater potential and higher reliability margin compared to Au and Pd-coated Cu wires.

  11. 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.

  12. Theoretical study of dynamic electron-spin-polarization via the doublet-quartet quantum-mixed state and time-resolved ESR spectra of the quartet high-spin state.

    PubMed

    Teki, Yoshio; Matsumoto, Takafumi

    2011-04-07

    The mechanism of the unique dynamic electron polarization of the quartet (S = 3/2) high-spin state via a doublet-quartet quantum-mixed state and detail theoretical calculations of the population transfer are reported. By the photo-induced electron transfer, the quantum-mixed charge-separate state is generated in acceptor-donor-radical triad (A-D-R). This mechanism explains well the unique dynamic electron polarization of the quartet state of A-D-R. The generation of the selectively populated quantum-mixed state and its transfer to the strongly coupled pure quartet and doublet states have been treated both by a perturbation approach and by exact numerical calculations. The analytical solutions show that generation of the quantum-mixed states with the selective populations after de-coherence and/or accompanying the (complete) dephasing during the charge-recombination are essential for the unique dynamic electron polarization. Thus, the elimination of the quantum coherence (loss of the quantum information) is the key process for the population transfer from the quantum-mixed state to the quartet state. The generation of high-field polarization on the strongly coupled quartet state by the charge-recombination process can be explained by a polarization transfer from the quantum-mixed charge-separate state. Typical time-resolved ESR patterns of the quantum-mixed state and of the strongly coupled quartet state are simulated based on the generation mechanism of the dynamic electron polarization. The dependence of the spectral pattern of the quartet high-spin state has been clarified for the fine-structure tensor and the exchange interaction of the quantum-mixed state. The spectral pattern of the quartet state is not sensitive towards the fine-structure tensor of the quantum-mixed state, because this tensor contributes only as a perturbation in the population transfer to the spin-sublevels of the quartet state. Based on the stochastic Liouville equation, it is also

  13. Surfactant-mediated layer-by-layer homoepitaxial growth of Cu/In/Cu(100) and Ag/Sb/Ag(111) systems: A theoretical study

    NASA Astrophysics Data System (ADS)

    Jiang, Ming; Zhao, Yu-Jun; Cao, Pei-Lin

    1998-04-01

    Two typical surfactant-mediated homoepitaxial metal systems, Cu/In/Cu(100) and Ag/Sb/Ag(111), are studied by using first-principles calculations and a kinetic Monte Carlo method. Our results confirm the validity of the model that Zhang and Lagally suggested for Cu/In/Cu(100) system. A repulsion model is proposed for the Ag/Sb/Ag(111) system where surface-substitutional Sb atoms repel diffusing Ag adatoms. The layer-by-layer growth for Ag/Sb/Ag(111) system is achieved with a repulsion model in kinetic Monte Carlo simulation. By comparing the two different growth models, the importance of the additional barrier ΔE and effectiveness of two ways of reducing ΔE are confirmed in determining film morphology.

  14. Djurleite (Cu1.94S) and low chalcocite (Cu2S): New crystal structure studies

    USGS Publications Warehouse

    Evans, H.T.

    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.

  15. 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.

  16. 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.

  17. 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.

  18. Low temperature studies in LiF:Mg,Cu,P.

    PubMed

    Mathur, V K; Bandyopadhyay, P K; Barkyoumb, J H; Cai, G G

    2002-01-01

    Despite extensive investigations carried out in LiF:Mg,Cu,P, the nature of the emission centre is not clearly understood. Results of X ray excited emission in this material at room temperature and at 16 K are presented to obtain more data that can throw light on the emission characteristics of this material. At room temperature only a single emission peak is seen around 390 nm but at 16 K the emission appears to consist of more than one emission band. The emission spectra could be fitted with three bands with peaks at 332, 385 and 447 nm. The X ray excited emission at 16 K after annealing at 573 K for 5 min suppresses the 332 nm emission but enhances 447 nm emission. Moreover, annealing at 573 K greatly reduces the emission intensity, which signifies that the luminescent centres are also destroyed in this process. Temperature-dependent X ray excited fluorescence below room temperature provides evidence of the existence of shallow traps, which give rise to a thermoluminescence peak around 130 K. On the basis of the present investigations it is proposed that the complex nature of the emission may be related to the formation of donor-acceptor pairs in this material. The possible nature of this donor-acceptor complex is discussed.

  19. Electronic structure calculations of ESR parameters of melanin units.

    PubMed

    Batagin-Neto, Augusto; Bronze-Uhle, Erika Soares; Graeff, Carlos Frederico de Oliveira

    2015-03-21

    Melanins represent an important class of natural pigments present in plants and animals that are currently considered to be promising materials for applications in optic and electronic devices. Despite their interesting properties, some of the basic features of melanins are not satisfactorily understood, including the origin of their intrinsic paramagnetism. A number of experiments have been performed to investigate the electron spin resonance (ESR) response of melanin derivatives, but until now, there has been no consensus regarding the real structure of the paramagnetic centers involved. In this work, we have employed electronic structure calculations to evaluate the ESR parameters of distinct melanin monomers and dimers in order to identify the possible structures associated with unpaired spins in this biopolymer. The g-factors and hyperfine constants of the cationic, anionic and radicalar structures were investigated. The results confirm the existence of at least two distinct paramagnetic centers in melanin structure, identifying the chemical species associated with them and their roles in electrical conductivity.

  20. Trap and recombination centers study in sprayed Cu2ZnSnS4 thin films

    NASA Astrophysics Data System (ADS)

    Courel, Maykel; Vigil-Galán, O.; Jiménez-Olarte, D.; Espíndola-Rodríguez, M.; Saucedo, E.

    2014-10-01

    In this work, a study of trap and recombination center properties in polycrystalline Cu2ZnSnS4 thin films is carried out in order to understand the poor performance in Cu2ZnSnS4 thin film solar cells. Thermally stimulated current has been studied in Cu2ZnSnS4 deposited by pneumatic spray pyrolysis method using various heating rates, in order to gain information about trap centers and/or deep levels present within the band-gap of this material. A set of temperature-dependent current curves revealed three levels with activation energy of 126 ± 10, 476 ± 25, and 1100 ± 100 meV. The possible nature of the three levels found is presented, in which the first one is likely to be related to CuZn antisites, while second and third to Sn vacancies and SnCu antisites, respectively. The values of frequency factor, capture cross section, and trap concentration have been determined for each center.

  1. ESR Detection of Frictional Heat in Seismic Fault Slip

    NASA Astrophysics Data System (ADS)

    Fukuchi, T.; Mizoguchi, K.; Shimamoto, T.

    2001-12-01

    Electron spin resonance (ESR) is a spectroscopic method to detect paramagnetic defect centers or impurities in materials. Fukuchi (2001) measured ESR spectra of the Nojima pseudotachylyte found along the Nojima fault that caused the 1995 Kobe Earthquake (M 7.2) in Japan. There has been controversy as to whether frictional melting or crushing is more essential for the origin of the Nojima pseudotachylyte. As a result of the ESR measurement, the Nojima pseudotachylyte gave a huge ESR signal of bulky trivalent iron (Fe3+) ions derived from ferrimagnetic iron oxides (γ -Fe2O3). It has turned out that the bulky Fe3+ ion signal is produced by heating the Nojima fault gouge and that the fault gouge changes from an ocherous paramagnetic material to a black ferrimagnetic one with heating. We carry out high-speed frictional experiments using a new rotary-shear high-speed frictional testing machine to confirm that frictional heat in faulting can produce the black material like pseudotachylyte. By shearing under the condition that the axial stress is 0.61 MPa, the equivalent speed is 1.74 m/s and the average displacement is about 15m, the fault gouge changes into the pseudotachylyte-like material with a strong bulky Fe3+ signal. From the fault gouge after the shearing, the traces of dehydration are observed along the shear plane. This means that hot fluids dehydrated by frictional heating pass through the fault gouge along the fault plane in natural faulting. Heat and mass transfer may occur with the hot fluid flow. Furthermore, we discuss how to estimate the temperature of frictional heat using the bulky Fe3+ signal. If we use the bulky Fe3+ signal detected from the Nojima pseudotachylyte, the maximum temperature in faulting is estimated as about 600° C. This result supports that the Nojima pseudotachylyte is a crushing-originated one. >http://www.cc.yamaguchi-u.ac.jp/~fukuchi/index.html

  2. 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.

  3. Morphology and etching studies on YBCO and CuO single crystals

    NASA Astrophysics Data System (ADS)

    Prabhakaran, D.; Subramanian, C.; Balakumar, S.; Ramasamy, P.

    1999-06-01

    Single crystals of YBCO (Y123) and CuO have been grown from a BaO-CuO (28:72) flux using a low axial gradient furnace (∼1°C/cm). Growth morphology of the grown crystals was studied using an optical microscope, scanning electron microscopy and atomic force microscopy. Cell parameter values and chemical composition of the grown crystals were determined from the X-ray diffraction data and inductively coupled plasma analysis, respectively. Etching studies were done for both the crystals using different etchants. Oxygen stoichiometry of the YBCO crystal was determined by iodometry titration analysis.

  4. Towards binding mechanism of Cu2+ on creatine kinase from Pelodiscus sinensis: molecular dynamics simulation integrating inhibition kinetics study.

    PubMed

    Cai, Yan; Lee, Jinhyuk; Wang, Wei; Park, Yong-Doo; Qian, Guo-Ying

    2017-02-27

    Cu2+ is well known to play important roles in living organisms having bifacial distinction: essential microelement that is necessary for a wide range of metabolic processes but hyper-accumulation of Cu2+ can be toxic. The physiological function of Cu2+ in ectothermic animals such as Pelodiscus sinensis (Chinese soft-shelled turtle) has not been elucidated. In this study, we elucidated effect of Cu2+ on the energy producing metabolic enzyme creatine kinase (CK), which might directly affect energy metabolism and homeostasis of P. sinensis. We first conducted molecular dynamics (MD) simulations between P-CK and Cu2+ and found that Cu2+ blocked the binding site of the ATP cofactor, indicating that Cu2+ could directly inactivate P-CK. We prepared the muscle type of CK (P-CK) and confirmed that Cu2+ conspicuously inactivated the activity of P-CK (IC50 = 24.3 µM) and exhibited non-competitive inhibition manner with creatine and ATP in a first-order kinetic process. This result was well matched to the MD simulation results that Cu2+-induced non-competitive inactivation of P-CK. The spectrofluorimetry study revealed that Cu2+ induced tertiary structure changes in P-CK accompanying with the exposure of hydrophobic surfaces. Interestingly, the addition of osmolytes (glycine, proline, and liquaemin) effectively restored activity of the Cu2+-inactivated P-CK. Our study illustrates the Cu2+-mediated unfolding of P-CK with disruption of the enzymatic function and the protective restoration role of osmolytes on P-CK inactivation. This study provides information of interest on P-CK as a metabolic enzyme of ectothermic animal in response to Cu2+ binding.

  5. 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.

  6. 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.

  7. Cu Doping in Ligand Free CdS Nanocrystals: Conductivity and Electronic Structure Study.

    PubMed

    Grandhi, G Krishnamurthy; Swathi, K; Narayan, K S; Viswanatha, Ranjani

    2014-07-03

    Ligand-free Cu-doped CdS nanocrystals (NCs) have been synthesized to elucidate their surface electronic structure. The Cu-doped ligand-free NCs unlike their undoped counterparts are shown to be luminescent. We used this Cu-related emission as a probe to study the nature of the surface trap states that results in negligible luminescence in the undoped NCs. The concentration of the sulfide ligands is shown to play a crucial role in the surface passivation of the NCs. Electrical conductivity of these NCs was also studied, and they were shown to exhibit significant conductivity of ∼10(-4) S cm(-1). Further we have shown that the electrical conductivity is closely correlated to the surface charge and hence the trap states of the individual NCs have far-reaching consequences in the device optimization.

  8. Ab-initio study of encapsulated and functionalized silicon nanotube with a monoatomically thin Cu wire

    NASA Astrophysics Data System (ADS)

    Chandel, Surjeet Kumar; Kumar, Arun; Ahluwalia, P. K.; Sharma, Raman

    2015-06-01

    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 2G0 and 4G0 respectively showing enhanced conductance for the functionalized SiNT.

  9. Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases.

    PubMed

    el-Ansary, Aida L; Abdel-Fattah, Hussein M; Abdel-Kader, Nora S

    2011-08-01

    The Schiff bases of N(2)O(2) dibasic ligands, H(2)La and H(2)Lb are prepared by the condensation of ethylenediamine (a) and trimethylenediamine (b) with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one. Also tetra basic ligands, H(4)La and H(4)Lb are prepared by the condensation of aliphatic amines (a) and (b) with 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one. New complexes of H(4)La and H(4)Lb with metal ions Mn(II), Ni(II) and Cu(II) are synthesized, in addition Mn(II) complexes with ligands H(2)La and H(2)Lb are also synthesized. Elemental and thermal analyses, infrared, ultraviolet-visible as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The structures of copper(II) complexes are also assigned based upon ESR spectra study. All the complexes separated with the stoichiometric ratio (1:1) (M:L) except Mn-H(4)La and Mn-H(4)Lb with (2:1) (M:L) molar ratio. In metal chelates of the type 1:1 (M:L), the Schiff bases behave as a dinegative N(2)O(2) tetradentate ligands. Moreover in 2:1 (M:L) complexes, the Schiff base molecules act as mono negative bidentate ligand and binuclear complex is then formed. The Schiff bases were assayed by the disc diffusion method for antibacterial activity against Staphylococcus aureus and Escherichia coli. The antifungal activity of the Schiff bases was also evaluated against the fungi Aspergillus flavus and Candida albicans.

  10. The Representation of Mixtures in the ESR Model for QM

    SciTech Connect

    Garola, Claudio; Sozzo, Sandro

    2010-05-04

    The extended semantic realism(ESR)model proposes a new theoretical perspective which embodies the mathematical formalism of Hilbert space quantum mechanics (QM) into a broader noncontextual, hence local, framework, reinterpreting quantum probabilities as conditional(in a nonstandard sense). We have proven in a previous paper that each generalized observable introduced by the ESR model is represented by a family of positive operator valued measures(POVM) parametrized by the pure states of the physical system OMEGA that is considered. We show here that each mixture is represented in the ESR model by a family of density operators parametrized by the physical properties characterizing OMEGA. This representation implies predictions that may differ from those of QM and avoids some deep problems that arise in the interpretation of mixtures provided by QM. We also show that the state transformations induced by idealized nondestructive measurements can be obtained by means of a nontrivial generalization of the Lueders postulate, and discuss our results in the special case of discrete generalized observables.

  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. Neutron scattering studies of YBa 2Cu 3O 6.6 and CuGeO 3

    NASA Astrophysics Data System (ADS)

    Shirane, G.

    1995-02-01

    A review is given of the current neutron scattering experiments at Brookhaven on two oxides containing spin ½ Cu 2+. The first topic is the search for incommensurate magnetic correlations in YBa 2Cu 3O 6.6 ( Tc = 46 K). Sternlieb et al. [Phys. Rev. B 50 (1994) 12915] have now established the energy-independent q line shape with characteristic flat tops. The second research topic is the new spin-Peierls transition in CuGeO 3 at 14 K, recently discovered by Hase et al. [Phys. Rev. Lett. 70 (1993) 3651]. A series of neutron measurements at Brookhaven have now established the Cu-oxygen coupled shifts, resulting in a dimerized singlet state. In addition, phonon measurements revealed an unusually soft longitudinal acoustic mode perpendicular to the chain direction.

  13. A study on brazing of Glidcop® to OFE Cu for application in Photon Absorbers of Indus-2

    NASA Astrophysics Data System (ADS)

    Yadav, D. P.; Kaul, R.; Ram Sankar, P.; Kak, A.; Ganesh, P.; Shiroman, R.; Singh, R.; Singh, A. P.; Tiwari, P.; Abhinandan, L.; Kukreja, L. M.; Shukla, S. K.

    2012-11-01

    The paper describes an experimental study aimed at standardizing brazing procedure for joining Glidcop to OFE Cu for its application in upgraded photon absorbers of 2.5 GeV synchrotron radiation source, Indus-2. Two different brazing routes, involving brazing with silver base (BVAg-8) and gold base (50Au/50Cu) alloys, were studied to join Glidcop to OFE Cu. Brazing with both alloys yielded helium leak tight and bakeable joints with acceptable shear strengths.

  14. Pressure- and Temperature-Dependent Study of Heusler Alloys Cu2MGa (M = Cr and V)

    NASA Astrophysics Data System (ADS)

    Gupta, Dinesh C.; Ghosh, Sukriti

    2017-04-01

    Full-potential computation of the electronic, magnetic, elastic and thermodynamic properties of Cu2MGa (M = Cr and V) alloys has been performed in the most stable Fm-3 m phase. The equilibrium lattice parameter is 5.9660 Å for Cu2CrGa and 5.9629 Å for Cu2VGa in the stable state. The application of mBJ potential has also found no energy gap in these alloys in either of the spin channels, hence they are metallic. The total and partial density of states, second-order elastic constants and their combinations are computed to show the electronic, magnetic, stability and brittle or ductile nature of these alloys, which are reported for the first time. Cauchy's pressure and Pugh's index predict Cu2CrGa to be brittle and Cu2VGa to be ductile. Both the materials are stiff enough to break. We have found that both the compounds are anisotropic, ferromagnetic and metallic in nature. We have used quasi-harmonic approximations to study the pressure and temperature variation of the thermodynamic properties of these alloys.

  15. 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.

  16. 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.

  17. 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.

  18. Sonochemical synthesis and mechanistic study of copper selenides Cu(2-x)Se, beta-CuSe, and Cu(3)Se(2).

    PubMed

    Xie, Yi; Zheng, Xiuwen; Jiang, Xuchuan; Lu, Jun; Zhu, Liying

    2002-01-28

    Nanocrystallites of nonstoichiometric copper selenide (Cu(2-x)Se) and stoichiometric copper selenides (beta-CuSe and Cu(3)Se(2)) were synthesized in different solutions via sonochemical irradiation at room temperature. The influence of solvents, surfactants, and ultrasonic irradiation on the morphology and phase of products has been investigated. The morphological difference of the products was mainly affected by the solvents and surfactants, which can self-aggregate into lamellar structures or microemulsions, and then these unique structures can act as both supramolecular template and microreactor to direct the growth of copper selenides. On the other hand, it was also found that the sonochemical irradiation and solvents played an important role in the formation of different phases of copper selenides. The proposed formation mechanism of copper selenides is discussed.

  19. STM/STS studies on vortex and electronic state in YBa 2Cu 3O y

    NASA Astrophysics Data System (ADS)

    Nishizaki, Terukazu; Shibata, Kenji; Maki, Makoto; Kobayashi, Norio

    2006-05-01

    Low temperature scanning tunneling microscopy (LT-STM) studies have been performed on the LT-cleaved and the chemically etched surface of YBa2Cu3Oy single crystals. We find that the vortex structure can be observed on the chemically etched surface of YBa2Cu3Oy as a function of temperature and magnetic field. At low magnetic fields, we observed a slightly distorted triangular lattice, which is attributed to the Bragg-glass phase. The triangular lattice transforms into a disordered structure in high magnetic fields above the order-disorder transition H∗(T). We observed that the disordered vortices form small clusters comprising 5- and 7-fold coordination pairs. These microscopically determined vortex structures are in good agreement with the vortex matter phase diagram derived from the macroscopic measurements, thus providing the evidence of the field-driven transition in the vortex solid phase of YBa2Cu3Oy.

  20. Pseudogap studied by optical conductivity spectra of Zn-substituted YBa2Cu3Oy

    NASA Astrophysics Data System (ADS)

    Uykur, Ece; Masui, Takahiko; Tanaka, Kiyohisa; Miyasaka, Shigeki; Tajima, Setsuko

    2012-02-01

    The pseudogap and the superconducting gap cause a similar suppression of the low energy optical conductivity, but the behaviors of the spectral weight transfers are different, which enables us to distinguish these two gaps. In the c-axis spectra of YBa2Cu3Oy, however, it is difficult to discuss these spectral weight transfers because of the additional structures due to a transverse Josephson plasma mode [1]. To overcome this problem, we substituted Zn for Cu, which is known to suppress those supplementary structures [2]. In this study, we performed temperature dependent reflectivity measurements in Zn-substituted YBa2Cu3Oy system. We have revealed the continuous transfer of the low energy spectral weight to the higher energy region even below Tc, which suggests the coexistence of the pseudogap and the superconducting gap. [1]C. Bernhard et al. Phys. Rev. B, 61 (2000) 618. [2]R. Hauff et al., Phys. Rev. Lett., 77 (1996) 4620.

  1. Effects of temperature on Cu structure deposited on Si substrate: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Hidayat, Aulia Fikri; Rosikhin, Ahmad; Syuhada, Ibnu; Winata, Toto

    2016-02-01

    The deposition process of copper onto silicon substrate was studied by the molecular dynamics method. Tersoff, MEAM, and Morse potentials were used to describe the interaction of Si-Si Cu-Cu, and Cu-Si, respectively. Deposition process was performed using NVE ensemble and applying Berendsen thermostat with 0,2 fs timestep for 100 ps. The effect of substrate temperature on the percentage of amorphous structure, radial distribution function (RDF), and coordination number was investigated. The result was indicated that at 300 K, the percentage of amorphous structure was relatively lower compared to another temperature. First peaks of RDF at each temperature were found at radius 3,05 Å and were still relatively wide, indicating short-range order structure.

  2. 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.

  3. Structural, compositional and Raman studies of ZnS: Ce, Cu co-doped nanoparticles

    NASA Astrophysics Data System (ADS)

    Harish, G. S.; Reddy, P. Sreedhara

    2013-06-01

    In this present work, Ce, Cu co-doped ZnS nanoparticles were prepared at room temperature using chemical precipitation method. The prepared nanoparticles were characterized by X-ray diffraction (XRD), Scanning Electron Microscope (SEM), Energy dispersive analysis of X-rays (EDAX) and High Resolution Raman spectroscopic techniques. X-ray diffraction studies show that the diameter of the particles is 2-4 nm. Broadened XRD peaks confirmed the formation of nanoparticles with face centered cubic (FCC) structure. SEM attached with EDS gave the size, morphology and compositional analysis of as-prepared material. The Raman spectra of unplanted and Cu, Ce ions implanted samples of nano structured ZnS showed LO mode and TO mode. Compared with the Raman modes (276 and 351 cm-1) of undoped ZnS nanoparticles, the Raman modes of Ce, Cu co-doped ZnS nanoparticles are slightly shifted towards lower frequency side.

  4. The EXL experiment at FAIR and plans with the ESR at GSI

    SciTech Connect

    Kalantar-Nayestanaki, N.

    2011-10-28

    In this contribution, the physics program of the EXL experiment at FAIR-NuSTAR along with its experimental setup will be briefly outlined. This experiment aims to study the structure and the dynamics of radioactive nuclei which collide with light ions in inverse kinematics. On the way to the final measurements, several measurements have been proposed at the existing ESR at GSI with the purpose of understanding the detection systems for EXL and obtaining the first physics results in this type of experiments in a storage ring.

  5. 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.

  6. 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.

  7. 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

  8. How Zn can impede Cu detoxification by chelating agents in Alzheimer's disease: a proof-of-concept study.

    PubMed

    Conte-Daban, Amandine; Day, Adam; Faller, Peter; Hureau, Christelle

    2016-10-04

    The role of Cu and Zn ions in Alzheimer's disease is linked to the consequences of their coordination to the amyloid-β (Aβ) peptide, i.e. to the modulation of Aβ aggregation and to the production of Reactive Oxygen Species (ROS), two central events of the so-called amyloid cascade. The role of both ions in Aβ aggregation is still controversial. Conversely the higher toxicity of the redox competent Cu ions (compared to the redox inert Zn ions) in ROS production is acknowledged. Thus the Cu ions can be considered as the main therapeutic target. Because Zn ions are present in higher quantity than Cu ions in the synaptic cleft, they can prevent detoxification of Cu by chelators unless they have an unusually high Cu over Zn selectivity. We describe a proof-of-concept study where the role of Zn on the metal swap reaction between two prototypical ligands and the Cu(Aβ) species has been investigated by several complementary spectroscopic techniques (UV-Vis, EPR and XANES). The first ligand has a higher Cu over Zn selectivity relative to the one of Aβ peptide while the second one exhibits a classical Cu over Zn selectivity. How Zn impacts the effect of the ligands on Cu-induced ROS production and Aβ aggregation is also reported.

  9. Adsorption on vicinal surfaces: {Pb}/{Cu(1,1,11) } — a TEAS study

    NASA Astrophysics Data System (ADS)

    Goapper, S.; Barbier, L.; Salanon, B.

    1996-08-01

    Pb adsorption on Cu(1,1,11) has been studied by He diffraction. Measurements of Pb cross-sections for He scattering as a function of coverage and temperature indicate a complex behavior of the absorbate. Dense island formation, preferential adsorption at steps and surface alloying effects were found.

  10. 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.

  11. 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.

  12. 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.

  13. NMR study of Cu2Se and Cu1.98Ag0.2Se superionic conductors

    NASA Astrophysics Data System (ADS)

    Sirusi Arvij, Ali; Ross, Joseph H., Jr.; Ballikaya, Sedat; Uher, Ctirad

    2015-03-01

    Cu2Se and Cu1.98Ag0.2Se are well known as superionic conductors and recently as thermoelectric materials due to observation of high ZT. We will report NMR of these compounds. Our results include indications of glassy anharmonic behavior at low temperatures, Cu ionic motion which becomes initiated near 90K, and motional narrowing near the phase transition at high temperatures as well as modified dynamics observed in the Ag-doped sample. NMR is particularly well suited to probe low frequency dynamics and at low temperatures the relaxation rate indicates anharmonic rattling behavior similar to what has been observed in other thermoelectric materials. A 90K change in the NMR spectra corresponds to the recently observed transport anomaly and indicates that the slow motion of Cu ions is initiated at this temperature and eventually becomes liquid-like at higher temperatures. We detect fast ionic motion in Cu2Se starting at 140K whereas in the Ag-doped compound this onset shifts to a higher temperature around 300K. At high temperatures the spectra become motionally narrowed, and we will discuss the narrowing and shifts in terms of activated carrier density and ionic motion. This work was supported by the Robert A. Welch Foundation.

  14. 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.

  15. Covellite CuS as a matrix for "invisible" gold: X-ray spectroscopic study of the chemical state of Cu and Au in synthetic minerals

    NASA Astrophysics Data System (ADS)

    Tagirov, Boris R.; Trigub, Alexander L.; Kvashnina, Kristina O.; Shiryaev, Andrey A.; Chareev, Dmitriy A.; Nickolsky, Maximilian S.; Abramova, Vera D.; Kovalchuk, Elena V.

    2016-10-01

    Geological processes leading to formation of sulfide ores often result in precipitation of gold-bearing sulfides which can contain high concentrations of this metal in "invisible" (or "refractory") state. Covellite (CuS) is ubiquitous mineral in many types of the ore deposits, and numerous studies of the natural ores show that covellite can contain high concentrations of Au. At the same time, Au-bearing covellite withstands cooling in contrast to other minerals of the Cu-Fe-S system (chalcocite, bornite, chalcopyrite), where Au exsolves at low temperatures. This makes covellite a convenient model system for investigation of the chemical state (local environment and valence) of the "invisible" Au in copper-sulfide ores (copper-porphyry, epithermal, volcanogenic massive sulfide, SEDEX deposits). Therefore, it is necessary to determine the location of Au in the covellite matrix as it will have important implications for the methods employed by mineral processing industry to extract Au from sulfide ores. Here we investigate the chemical state of Cu and Au in synthetic covellite containing up to 0.3 wt.% of Au in the "invisible" state. The covellite crystals were synthesized by hydrothermal and salt flux methods. Formation of the chemically bound Au is indicated by strong dependence of the concentration of Au in covellite on the sulfur fugacity in the experimental system (d(log C(Au))/d(log f(S2)) ∼ 0.65). The Au concentration of covellite grows with increasing temperature from 400 to 450 °C, whereas further temperature increase to 500 °C has only minor effect. The synthesized minerals were studied using X-ray absorption fine structure spectroscopy (XAFS) in high energy resolution fluorescence detection (HERFD) mode. Ab initio simulations of Cu K edge XANES spectra show that the Cu oxidation state in two structural positions in covellite (tetrahedral and triangular coordination with S atoms) is identical: the total loss of electronic charge for the 3d shell is ∼0

  16. 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+).

  17. 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

  18. Synthesis and characterization of Co(II), Ni(II) and Cu(II) complexes involving hydroxy antipyrine azodyes

    NASA Astrophysics Data System (ADS)

    Gaber, M.; Hassanein, A. M.; Lotfalla, A. A.

    2008-03-01

    The complexes formed between some hydroxy antipyrine azodyes and Co(II), Ni(II) and Cu(II) ions were studied spectrophotometrically in solution. The stoichiometry and stability constants of the metal chelates were determined. The spectrophotometric determination of the titled metal ions and titration using EDTA were reported. The chelating behaviour of the azodyes was confirmed by preparing the solid chelates in which their structures are elucidated using molar conductance, elemental, thermogravimetric (TGA) analyses, IR, ESR and electronic spectra as well as the magnetic measurements. Kinetic parameters are computed from the thermal decomposition data. The electrical properties for the metal complexes are measured from which the activation energies are calculated.

  19. Study of the nanocrystalline ball-milled Cu80(Fe0.3Co0.7)20 compound

    NASA Astrophysics Data System (ADS)

    Galdeano, S.; Mathon, M. H.; Chaffron, L.; André, G.; Vincent, E.; Traverse, A.; de Novion, C. H.

    The influence of the ball-milling temperature and intensity has been studied on the nanostructure of the Cu80(Fe0.3Co0.7)20 compound. The ball milling of mixed powders of Cu-Fe and Cu-Co supersaturated solid solutions allows the formation of a very fine Fe30Co70 precipitation in the Cu matrix, interesting for its magnetoresistive properties. Powder neutron diffraction and SANS, coupled to magnetic measurements and EXAFS experiments, allowed us to correlate the ball-milling conditions to the nanostructure and the magnetic properties of the ternary compound.

  20. Luminescence study of γ-ray and C5+ ion beam-irradiated LiCaBO3:Cu phosphor

    NASA Astrophysics Data System (ADS)

    Oza, Abha H.; Dhoble, N. S.; Lochab, S. P.; Dhoble, S. J.

    2015-07-01

    Cu-doped LiCaBO3 phosphors were prepared by modified solid-state synthesis and the formation of compound was confirmed by X-ray diffraction study. LiCaBO3:Cu+ (Cu = 0.02, 0.05, 0.1 and 0.2 mol%) were studied for photoluminescence (PL) study and prominent PL emission spectra were obtained for Cu+ with transition 3d94s1 → 3d10. The phosphors were further studied by thermoluminescence (TL) property for exposure to γ-ray irradiation of 1.2 rad with 137Cs source. TL of LiCaBO3:Cu was also studied for C5+ (3.75 × 1012 ion cm-2) beam irradiation for 1 min exposure time. Trapping parameters (activation energy and frequency factor) for single deconvoluted peaks were obtained by Chen's peak shape method.

  1. 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

  2. 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

  3. ESR dating of tooth enamel: comparison with {230Th }/{234U } speleothem dates at La Chaise-de-Vouthon (Charente), France

    NASA Astrophysics Data System (ADS)

    Blackwell, Bonnie; Porat, N.; Schwarcz, H. P.; Debénath, A.

    source of error lies in the difficulty in modelling the external γ dose. Only U leaching, not incorrectly modelled U uptake, would cause the underestimation. Diagenetic alteration may also cause anomalous fading, thermal instability, variation in k, or ESR signal suppression. More study into the effects of diagenesis alteration on enamel ESR signals is needed, as is a reevaluation of the mean signal life and α efficiency for several more enamel samples.

  4. The mining chemical Polydadmac is cytotoxic but does not interfere with Cu-induced toxicity in Atlantic salmon hepatocytes.

    PubMed

    Olsvik, Pål A; Berntssen, Marc H G; Waagbø, Rune; Hevrøy, Ernst; Søfteland, Liv

    2015-12-25

    To speed up sedimentation of suspended solids the mining industry often uses flocculent chemicals. In this work we evaluated the cytotoxic and mechanistic effects of Polydadmac, and its basic component Dadmac, on fish cells. Dose-response effects, temperature-dependent effects and impact of Dadmac and Polydadmac on Cu toxicity were studied in Atlantic salmon hepatocytes. We used the xCELLigence system and the MTT test for cytotoxicity assessments, and real-time RT-qPCR to evaluate molecular effects. The results showed a cytotoxic response for Polydadmac but not for Dadmac. Elevated levels of Cu were cytotoxic. Moderately cytotoxic concentrations of Cu (100-1000 μM) induced significant responses on the transcription of a number of genes in the cells, i.e. cuznsod (sod1), cat, mnsod (sod2), nfe2l2, hmox1, mta, casp3b, casp6, bclx, cyp1a, ccs, atp7a, app, mmp13, esr1, ppara, fads2 and ptgs2. A factorial PLS regression model for mnsod transcription showed a synergistic effect between Dadmac and Cu exposure in the cells, indicating an interaction effect between Dadmac and Cu on mitochondrial ROS scavenging. No interaction effects were seen for Polydadmac on Cu toxicity. In conclusion, Polydadmac is cytotoxic at elevated concentrations but appears to have low ability to interfere with Cu toxicity in Atlantic salmon liver cells.

  5. 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.

  6. Study on the adsorption of Cu(II) by folic acid functionalized magnetic graphene oxide

    NASA Astrophysics Data System (ADS)

    Wang, Cuicui; Ge, Heyi; Zhao, Yueying; Liu, Shanshan; Zou, Yu; Zhang, Wenbo

    2017-02-01

    The folic acid functionalized magnetic graphene oxide (FA-mGO) as a new adsorbent has been synthesized in this work for the elimination of Cu(II) from waste water. The as-prepared FA-mGO was tested by SEM, TEM, particle size analyzer, FTIR, XRD, Roman spectrum, TGA and magnetic properties analyzer. Some factors, such as adsorbent dose, pH, contact time, initial concentration of adsorbate and temperature were explored. The results showed that the FA-mGO had the better adsorption performance than mGO. After 40 min, the adsorption equilibrium could be reached. Furthermore, the adsorption property obeyed the pseudo-second order kinetic model and the Temkin isotherms well. The maximum adsorption capacity was 283.29 mg/g for Cu(II) from Pseudo-second-order model at pH=5 and 318 K. The chelation action between FA and Cu(II) along with electrostatic incorporation between GO and Cu(II) determined the favourable adsorption property. Besides, thermodynamic studies results ∆G0<0, ∆H0>0, ∆S0>0 suggested that the adsorption mechanism was an endothermic and spontaneous process essentially. Finally, desorption and reusability studies imply FA-mGO has an excellent reproducibility and is benefit to environmental protection and resource conservation.

  7. Magnetic excitations in the spin-1/2 triangular-lattice antiferromagnet Cs2CuBr4

    DOE PAGES

    Zvyagin, S. A.; Ozerov, M.; Kamenskyi, D.; ...

    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

  8. 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

  9. K-edge EXAFS and XANES studies of Cu in CdTe thin-film solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Xiangxin; Gupta, Akhlesh; Compaan, Alvin D.; Leyarovska, Nadia; Terry, Jeff

    2002-03-01

    Copper has been identified as a very important dopant element in CdTe thin-film solar cells. Cu is a deep acceptor in CdTe and is commonly used to obtain a heavily doped, low resistance back contact to polycrystalline CdTe. Cu also helps to increase the open circuit voltage of the cell. However, Cu is also a fast diffuser in CdTe, especially along grain boundaries, and can accumulate at the CdS/CdTe junction. It is suspected of leading to cell performance degradation in some cases. The present study is designed to help identify the lattice location of the Cu in CdTe. Cu K-edge, x-ray absorption (XAS) measurements were conducted on Cu in thin films of CdTe. Experiments were performed at the MR-CAT beamline at the Advanced Photon Source. The 3 mm CdTe layers were magnetron sputtered onto fused silica substrates. Some films were diffused with Cu from a 200 Å layer of evaporated Cu. XAS spectra were collected in fluorescence geometry with a 13 elements Ge detector. Quantitative fluorescence spectroscopy measurements were also performed. Details of the Cu environment and possible changes with time will be reported.

  10. Photocatalytic degradation of methylene blue by TiO2-Cu thin films: theoretical and experimental study.

    PubMed

    Carvalho, Hudson W P; Batista, Ana P L; Hammer, Peter; Ramalho, Teodorico C

    2010-12-15

    In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nm thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1s to 100°C and 400°C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations.

  11. ESR (Electroslag Refining) Steel Deoxidation and Slag Practice - Influence on Inclusion Morphology,

    DTIC Science & Technology

    1984-01-01

    VICTORIA I REPORT MRL-R-915 ESR STEEL DEOXIDATION AND SLAG PRACTICE - INFLUENCE ON INCLUSION MORPHOLOGY G.M. Weston and R.C. Andrew THE UNITED...Commonweallh of Austaii eJA3UAY, 1984 DEPARTMENT OF DEFENCE MATERIALS RESEARCH LABORATORIES REPORT MRL-R-915 ESR STEEL DEOXIDATION AND SLAG PRACTICE...TLE ESR STEEL DEOXIDATION AND SLAG PRACTICE - INFLUENCE ON INCLUSION MORPHOLOGY AUTHOR(S) CORPORATE AUTHOR Materials Research Laboratories G.M. Weston

  12. 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.

  13. 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.

  14. 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.

  15. LEED - IV and DFT study of the co-adsorption of chlorine and water on Cu(100)

    NASA Astrophysics Data System (ADS)

    Puisto, M.; Pussi, K.; Alatalo, M.; Hesp, D.; Dhanak, V. R.; Lucas, C. A.; Grunder, Y.

    2017-03-01

    We have studied the adsorption of water on a Cl covered Cu(100) surface using both low energy electron diffraction (LEED) experiments and density functional theory (DFT) calculations. On the Cu{100}-c(2×2)-Cl surface water is shown to form a bilayer, which is weakly bound to the surface.

  16. Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study

    NASA Astrophysics Data System (ADS)

    Jiang, Zhao; Qin, Pei; Fang, Tao

    2017-02-01

    The study of formic acid decomposition on transition metal surfaces is important to obtain useful information for vapor phase catalysis involving HCOOH and for the development of direct formic acid fuel cells. In this study, periodic density functional theory calculations have been employed to investigate the dissociation pathways of HCOOH on Cu (111) surface. About adsorption, it is found that the adsorption of HCOO, COOH, HCO, CO, OH and H on Cu (111) are considered chemisorption, whereas HCOOH, CO2, H2O and H2 have the weak interaction with Cu (111) surface. Furthermore, the minimum energy pathways are analyzed for the decomposition of HCOOH to CO2 and CO through the scission of Hsbnd O, Csbnd H and Csbnd O bonds. It is found that HCOOH, HCOO and COOH prefer to dissociate in the related reactions rather than desorb. For the decomposition, it is indicated that HCO and COOH are the main dissociated intermediates of trans-HCOOH, CO2 is the main dissociated intermediates of bidentate-HCOO, and CO is the main dissociated product of cis-COOH. The co-adsorbed H atom is beneficial for the formation of CO2 from cis-COOH. Besides, it is found that the most favorable path for HCOOH decomposition on Cu (111) surface is HCOOH-HCO-CO (Path 5), where the step of CO formation from HCO dehydrogenation is considered to be the rate-determining step. The results also show that CO is preferentially formed as the dominant product of HCOOH on Cu (111) surface.

  17. 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† †Electronic supplementary information (ESI) available: Additional electrochemical and spectroscopic results, mass spectrometry study, and DFT-optimized Cartesian coordinates. See DOI: 10.1039/c5an01129a Click here for additional data file.

    PubMed Central

    Machata, Peter; Clikeman, Tyler T.; Rosenkranz, Marco

    2015-01-01

    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

  18. Detection of gamma-irradiated peanuts by ESR spectroscopy and GC analysis of hydrocarbons

    NASA Astrophysics Data System (ADS)

    Ming Li, Wei; Li, An; Ming Ha, Yi; Wang, Feng; Li Zhang, Yan

    2011-03-01

    Peanuts were analyzed by electron spin resonance (ESR) spectroscopy and gas chromatography (GC) before and after gamma irradiation. Using European protocols, the validity and effectiveness of these two techniques were compared with regard to sample preparation, sample and solvent consumption and dose-response curves after irradiation. The results showed the possibility of using ESR and GC for distinguishing between irradiated and unirradiated peanuts. A radiation dose of 0.1 kGy could be detected by ESR but not by GC. The results also indicated that GC is an effective method for qualitative analysis of irradiated peanut, while ESR is suitable for the rapid detection of irradiated peanuts.

  19. ESR (Electroslag Refining) Technology in Australia - Laboratory Research and Industrial Development,

    DTIC Science & Technology

    1983-07-01

    A typical inclusion rating for this steel is given for ingot ESR 4340 -2 Table 13. It can be concluded that although inclusion modification may improve...LEVELS -S. STEEL GRADE CLEANLINESS (ASTM E45-METHOD D-WORST FIELD RATING) A B C D -. +EF AISI 4140 2.OOH 0.30HT 0 0.70T ESR AISI 4340 -1 0.60H 0 0 1.OOT ESR ...I * 7-j777’T77:- 7 77777 -Y FIG. I Rippled surface of ingots of ESR low alloy steel , AISI 4340 remuelted using high-silica, five -component s

  20. Effect of Spot and Stud Welding on ESR 4340 Steel Armor.

    DTIC Science & Technology

    1978-02-01

    ESR ) 4340 steel armor. MATERIALS The armor used in this program was commercially produced ESR 4340 steeL in thicknesses of...N — AO—AO5k 025 ARMY MATERIALS AND MECHANICS RESEARCH CENTER WATERTO——ETC F/S 13/5 EFFECT OF SPOT AND STUD WELDING ON ESR 14314 0 STEEL ARMOR. (U...5 lAD I ~ EFFECT OF SPOT~AND STUD WELDING ON ESR 434O~ STEEL ARMOR~ ~~ - /, ‘ , ~ . ~~~ — ~ — ~~~ — , ~~~~~~ ——-...—- ( -~~/ ~~~ - ‘~/ ~~~ ‘ .

  1. 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.

  2. Association of ESR1 and C6orf97 gene polymorphism with osteoporosis in postmenopausal women.

    PubMed

    Luo, Lianmei; Xia, Weibo; Nie, Min; Sun, Yue; Jiang, Yan; Zhao, Jing; He, Shuli; Xu, Ling

    2014-05-01

    The estrogen receptor 1 (ESR1) and Chromosome 6 Open Reading Frame 97 (C6orf97) gene polymorphisms were earlier reported to be associated with osteoporosis in the European cohort. The aim of this study was to investigate the association of four single nucleotide polymorphisms (SNP) with bone mineral density (BMD), fracture, vertebral fracture, bone turnover or 25-hydroxyvitamin D [25(OH)D] in 1,753 randomly selected postmenopausal women in China. Vertebral fracture, BMD of lumbar spine (2-4), femoral neck and total hip were measured respectively. Serum N-terminal procollagen of type 1 collagen (P1NP), β-isomerized type I collagen C-telopeptide breakdown products (β-CTX) and 25(OH)D3 were also determined. Binary logistic regression revealed significant associations between fracture risk with rs1999805 (P=0.041, OR 1.633, 95%CI 1.020-2.616) and rs6929137 (P=0.005, OR 1.932, 95%CI 1.226-3.045) in recessive model. Significant association was also observed between vertebral fracture risk and rs1038304 (P=0.039, OR 0.549, 95%CI 0.311-0.969) in recessive model. Liner regression analyses showed that only the CC group of rs4870044 was significantly associated with total hip in dominant model (P=0.034). Our findings suggest that ESR1 and C6orf97 gene polymorphism is associated with fracture and vertebral fracture risk in Chinese postmenopausal women.

  3. 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.

  4. Scanning Tunneling Microscopy Studies of Surface Structures of Icosahedral Al-Cu-Fe Quasicrystals

    SciTech Connect

    Cai, Tanhong

    2001-01-01

    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.

  5. Studies on the interaction between 9-fluorenylmethyl chloroformate and Fe3+ and Cu2+ ions: spectroscopic and theoretical calculation approach.

    PubMed

    Gu, Zhenyan; Lei, Wu; Shi, Wenyan; Hao, Qingli; Si, Weimeng; Xia, Xifeng; Wang, Fengxiang

    2014-11-11

    The interaction between 9-fluorenylmethyl chloroformate (FMOC-Cl) and Fe3+ and Cu2+ ions was investigated using fluorescence, UV/Vis absorption spectroscopies and theoretical calculation. The optical property of FMOC-Cl was studied in detail in absence and presence of various transition metal ions with particular affinity to Fe3+ and Cu2+ ions. With the fluorescence characteristic band centered at 307 and 315 nm for FMOC-Cl, the introduction of Fe3+ or Cu2+ ions leads to the fluorescence quenching of FMOC-Cl with different shift and intensities of two fluorescent bands. It allows us to differentiate between FMOC-Cl and Fe3+ and Cu2+ ions interaction behavior. The study on fluorescent kinetics confirms that the fluorescence quenching of FMOC-Cl with Fe3+ and Cu2+ ions is based on the formation of non-fluorescent material, that is, static quenching. Further analyses of bond lengths, Mulliken atomic charges and the frontier orbital compositions for FMOC-Cl and its complexes with Fe3+ and Cu2+ ions were carried out. The theoretical calculations prove the fluorescence quenching originates from the formation of coordination bonds between the oxygen atom of the carbonyl group of FMOC-Cl and Fe3+ and Cu2+ ions. The commercially available FMOC-Cl can be used as excellent fluorescent probe toward Fe3+ and Cu2+ ions with high sensitivity.

  6. Studies on the interaction between 9-fluorenylmethyl chloroformate and Fe3+ and Cu2+ ions: Spectroscopic and theoretical calculation approach

    NASA Astrophysics Data System (ADS)

    Gu, Zhenyan; Lei, Wu; Shi, Wenyan; Hao, Qingli; Si, Weimeng; Xia, Xifeng; Wang, Fengxiang

    2014-11-01

    The interaction between 9-fluorenylmethyl chloroformate (FMOC-Cl) and Fe3+ and Cu2+ ions was investigated using fluorescence, UV/Vis absorption spectroscopies and theoretical calculation. The optical property of FMOC-Cl was studied in detail in absence and presence of various transition metal ions with particular affinity to Fe3+ and Cu2+ ions. With the fluorescence characteristic band centered at 307 and 315 nm for FMOC-Cl, the introduction of Fe3+ or Cu2+ ions leads to the fluorescence quenching of FMOC-Cl with different shift and intensities of two fluorescent bands. It allows us to differentiate between FMOC-Cl and Fe3+ and Cu2+ ions interaction behavior. The study on fluorescent kinetics confirms that the fluorescence quenching of FMOC-Cl with Fe3+ and Cu2+ ions is based on the formation of non-fluorescent material, that is, static quenching. Further analyses of bond lengths, Mulliken atomic charges and the frontier orbital compositions for FMOC-Cl and its complexes with Fe3+ and Cu2+ ions were carried out. The theoretical calculations prove the fluorescence quenching originates from the formation of coordination bonds between the oxygen atom of the carbonyl group of FMOC-Cl and Fe3+ and Cu2+ ions. The commercially available FMOC-Cl can be used as excellent fluorescent probe toward Fe3+ and Cu2+ ions with high sensitivity.

  7. First principle study of the electronic structure, Fermi surface, electronic charge density and optical properties of ThCu5In and ThCu5Sn single crystals

    NASA Astrophysics Data System (ADS)

    Reshak, A. H.; Azam, Sikander

    2014-02-01

    The electronic structure, Fermi surface, electronic charge density and optical properties of ThCu5In and ThCu5Sn single crystals are studied. The calculations are based on the full potential-linearized augmented plane wave (FPLAPW) method. The exchange and correlation potential is treated by the local density approximation (LDA) and generalized-gradient approximation (GGA), in addition the Engel-Vosko (EV-GGA) formalism was also applied. The DFT calculations show that these compounds have metallic origin. The contribution of different bands was analyzed from total and partial density of states curves. The values of the density of states at Fermi energy (N(EF)) for ThCu5In (ThCu5Sn) is 1.75 (1.63) states/eV unit cell. The bare electronic specific heat coefficient (γ) is found to be equal to 0.30 and 0.28 mJ/mol-K2 for ThCu5In and ThCu5Sn, respectively. The Fermi surface of ThCu5In/ThCu5Sn is composed of three/four bands crossing along the R-Γ direction. The bonding features are analyzed by using the electronic charge density contour in the (101) crystallographic plane and it shows the covalent character of Cu-Cu and Sn/In-Cu bonds. The optical properties were also calculated and analyzed.

  8. Transition from exo- to endo- Cu absorption in CuSin clusters: A Genetic Algorithms Density Functional Theory (DFT) Study

    PubMed Central

    Oña, Ofelia B.; Ferraro, Marta B.; Facelli, Julio C.

    2010-01-01

    The characterization and prediction of the structures of metal silicon clusters is important for nanotechnology research because these clusters can be used as building blocks for nano devices, integrated circuits and solar cells. Several authors have postulated that there is a transition between exo to endo absorption of Cu in Sin clusters and showed that for n larger than 9 it is possible to find endohedral clusters. Unfortunately, no global searchers have confirmed this observation, which is based on local optimizations of plausible structures. Here we use parallel Genetic Algorithms (GA), as implemented in our MGAC software, directly coupled with DFT energy calculations to show that the global search of CuSin cluster structures does not find endohedral clusters for n < 8 but finds them for n ≥ 10. PMID:21785526

  9. Study of Cu ions acceleration via UV laser ablation

    NASA Astrophysics Data System (ADS)

    Belloni, F.; Doria, D.; Lorusso, A.; Nassisi, Vincenzo; Torrisi, Lorenzo

    2005-03-01

    In this work an ion acceleration system based on a laser ion source was studied. It was able to generate ion beams utilizing as a source a laser plasma produced by a XeCl laser from a copper target. The focused laser beam provided a power density on the target surface of about 3.5x108 W/cm2. Laser wavelength and pulse duration were 308 nm and 20 ns, respectively. The experimental apparatus consisted substantially of a plasma generation chamber, a drift tube and an expansion chamber mounted on the target stem inside the generation chamber. The expansion chamber end formed the acceleration gap together with a grounded bored electrode, placed in front of it at a distance of 1.3 cm. A Faraday cup placed at the end of the drift tube was used to reveal the ion intensity. Many attempts were done in order to accelerate plasma ions without the expansion chamber, but arcs were present. The maximum accelerating voltage applied to the extraction gap was 18 kV, resulting in an ion bunch of about 4.2 nC and a peak current of 220 μA.

  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. 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⊥.

  12. Molecular Dynamics Study of Surface Anisotropy in Ag_{60} Cu_{40} Alloy at Nanoscale

    NASA Astrophysics Data System (ADS)

    Imran, Muhammad; Hussain, Fayyaz; Rashid, Muhammad; Kousar, Farhana; Javid, M. Arshad; Ullah, Hafeez; Ahmad, Ejaz; Ahmad, S. A.

    2017-03-01

    In the present study, molecular dynamics simulation has been performed to investigate the anisotropic behavior of free standing Ag_{60} Cu_{40} nanorods. We choose different orientations with various cross sections to study the dynamics of thermal behavior of Ag_{60} Cu_{40} nanorods. The system is modeled using embedded atom method potentials. The radial distribution functions are analyzed to reveal the dynamic evolution of the structural behavior of nanorods with different orientations and sample sizes. The total energy and mean square displacement is also calculated to characterize the melting phenomenon of various samples. The melting temperature of the nanorods is found to be significantly size and orientation dependent, and it increases with the increase in cross-sectional area. The nanorods with low-index crystallographic surfaces such as (110) exhibit lowest melting temperature as compared to compact surfaces (111).

  13. ESR1 mutations in circulating plasma tumor DNA from metastatic breast cancer patients

    PubMed Central

    Chu, David; Paoletti, Costanza; Gersch, Christina; VanDenBerg, Dustin A.; Zabransky, Daniel J.; Cochran, Rory L.; Wong, Hong Yuen; Toro, Patricia Valda; Cidado, Justin; Croessmann, Sarah; Erlanger, Bracha; Cravero, Karen; Kyker-Snowman, Kelly; Button, Berry; Parsons, Heather; Dalton, W. Brian; Gillani, Riaz; Medford, Arielle; Aung, Kimberly; Tokudome, Nahomi; Chinnaiyan, Arul M.; Schott, Anne; Robinson, Dan; Jacks, Karen S.; Lauring, Josh; Hurley, Paula; Hayes, Daniel F.; Rae, James; Park, Ben Ho

    2016-01-01

    Purpose Mutations in the estrogen receptor-alpha (ER) gene, ESR1, have been identified in breast cancer metastases after progression on endocrine therapies. Due to limitations of metastatic biopsies, the reported frequency of ESR1 mutations may be underestimated. Here, we show a high frequency of ESR1 mutations using circulating plasma tumor DNA (ptDNA) from metastatic breast cancer patients. Experimental Design We retrospectively obtained plasma samples from eight patients with known ESR1 mutations and three patients with wild type ESR1 identified by next generation sequencing (NGS) of biopsied metastatic tissues. Three common ESR1 mutations were queried for using droplet digital polymerase chain reaction (ddPCR). In a prospective cohort, metastatic tissue and plasma were collected contemporaneously from eight ER-positive and four ER-negative patients. Tissue biopsies were sequenced by NGS and ptDNA ESR1 mutations were analyzed by ddPCR. Results In the retrospective cohort, all corresponding mutations were detected in ptDNA, with two patients harboring additional ESR1 mutations not present in their metastatic tissues. In the prospective cohort, three ER-positive patients did not have adequate tissue for NGS, and no ESR1 mutations were identified in tissue biopsies from the other nine patients. In contrast, ddPCR detected seven ptDNA ESR1 mutations in six of twelve patients (50%). Conclusions We show that ESR1 mutations can occur at a high frequency and suggest that blood can be used to identify additional mutations not found by sequencing of a single metastatic lesion. PMID:26261103

  14. 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.

  15. A computational study of the quantum transport properties of a Cu-CNT composite.

    PubMed

    Ghorbani-Asl, Mahdi; Bristowe, Paul D; Koziol, Krzysztof

    2015-07-28

    The quantum transport properties of a Cu-CNT composite are studied using a non-equilibrium Green's function approach combined with the self-consistent-charge density-functional tight-binding method. The results show that the electrical conductance of the composite depends strongly on CNT density and alignment but more weakly on chirality. Alignment with the applied bias is preferred and the conductance of the composite increases as its mass density increases.

  16. First-Principles Study of the Role of Cu in Improving the Coercivity of Nd-Fe-B Permanent Magnets

    NASA Astrophysics Data System (ADS)

    Tatetsu, Y.; Tsuneyuki, S.; Gohda, Y.

    2016-12-01

    We study the magnetic and electronic properties of Cu-doped Nd2 Fe14 B /NdOx systems with first-principles calculations in order to understand the roles of Cu in improving the coercivity of Nd-Fe-B permanent magnets. By analyzing the formation energies of several model systems, we find that Cu prefers to be at the interface. We conclude that the Cu addition to Nd-Fe-B magnets is a practical way of not only increasing the anisotropy of Nd atoms at the interface but also of lessening the magnetic coupling between the Nd and Fe atoms. Particularly, substituting Fe at the interface of the main phase with Cu works effectively in terms of improving the magnetic anisotropy in Nd atoms. This may explain the coercivity improvements reported recently.

  17. Theoretical study on the composition location of the best glass formers in Cu-Zr amorphous alloys.

    PubMed

    Wang, Da; Zhao, Shi-Jin; Liu, Li-Min

    2015-01-29

    This study combines the molecular dynamics (MD) simulations and first-principles approach to explain the experimental observation that the best glass formers of Cu-Zr bulk metallic glasses (BMGs) have the compositions Cu50Zr50 and Cu64Zr36. These two best glass formers are first calculated to be most abundantly composed of Cu6Zr7 and Cu8Zr5 icosahedral clusters when compared in the compositional range of CuxZr100-x (45 ≤ x ≤ 70), and then these two icosahedral clusters are calculated to have the lowest formation energy among the icosahedral clusters CuxZr13-x (3 ≤ x ≤ 10), as well as possessing some characteristics in electronic structure and chemical hardness. Through understanding the properties of specific icosahedral clusters in metallic glasses, the structural and energetic contribution to the glass-forming ability are systematically discussed.

  18. Creation of Cu2O@TiO2 composite photocatalysts with p-n heterojunctions formed on exposed Cu2O facets, their energy band alignment study, and their enhanced photocatalytic activity under illumination with visible light.

    PubMed

    Liu, Lingmei; Yang, Weiyi; Sun, Wuzhu; Li, Qi; Shang, Jian Ku

    2015-01-28

    The creation of photocatalysts with controlled facets has become an important approach to enhance their activity. However, how the formation of heterojunctions on exposed facets could affect their photocatalytic performance ranking had not yet been investigated. In this study, Cu2O@TiO2 core-shell structures were created, and Cu2O/TiO2 p-n heterojunctions were formed on various exposed facets of Cu2O cubes, Cu2O cuboctahedra, and Cu2O octahedra, respectively. These Cu2O@TiO2 polyhedra demonstrated an enhanced photocatalytic degradation effect on Methylene Blue (MB) and 4-nitrophenol (4-NP) under visible light illumination, because of the enhanced charge carrier separation by the formation of Cu2O@TiO2 p-n heterojunctions. It was further found that their photocatalytic performance was also facet-dependent as pure Cu2O polyhedra, while the photocatalytic performance ranking of these Cu2O@TiO2 polyhedra was different with that of their corresponding Cu2O polyhedron cores. By the combination of optical property measurement and XPS analysis, the energy band alignments of these Cu2O@TiO2 polyhedra were determined, which demonstrated that Cu2O@TiO2 octahedra had the highest band offset for the separation of charge carriers. Thus, the charge-carrier-separation-driven force in Cu2O@TiO2 polyhedra was different from their corresponding Cu2O polyhedron cores, which resulted in their different surface photovoltage spectrum (SPS) responses and different photocatalytic performance rankings.

  19. Study of Cu-related Defect States in Single-crystal CdTe

    NASA Astrophysics Data System (ADS)

    Corwine, Caroline; Sites, James; Gessert, Timothy; Metzger, Wyatt; Dippo, Pat; Duda, Anna

    2003-10-01

    We have studied single-crystal CdTe using low-temperature photoluminescence (PL) in an effort to understand the effects of copper on the deep levels, as well as the effect of a bromine methanol (BrMe) etch on subsequent copper diffusion into CdTe. In present polycrystalline CdS/CdTe solar cell technology, the use of a back contact that contains Cu is necessary to produce high-efficiency cells. However, it is not generally understood why Cu is necessary for these devices to function well. In order to obtain further advances in the efficiencies of these solar cells, it is important to know how the back contact process may affect the defect states in CdTe. PL is one tool used to study defect states. However, before PL can be used effectively for polycrystalline CdTe solar cells, relevant spectral features first must be interpreted for single-crystal CdTe. All PL in this study was taken at 4.5 K. We report on PL peaks at 1.40 and 1.45 eV, which are seen only after Cu is diffused into single-crystal CdTe.

  20. 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.

  1. 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.

  2. Morphological and Structural Changes During the Reduction and Reoxidation of CuO/CeO(2) and Ce(1-x)Cu(x)O(2) Nanocatalysts: In-situ Studies with Environmental TEM, XRD and XAS

    SciTech Connect

    Rodriguez, J.A.; Ciston, J.; Si, R.; Hanson, J.C.; Martínez-Arias, A.; Fernandez-García, M.; Zhu, Y.

    2011-07-21

    We have studied the structural, morphological, and electronic properties of CuO/CeO{sub 2} and Ce{sub 1-x}Cu{sub x}O{sub 2} nanocatalysts during reduction/oxidation cycles using H{sub 2} and O{sub 2} as chemical probes. Time-resolved in situ characterization was performed by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) as well as aberration-corrected environmental transmission electron microscopy (ETEM). We have found that both types of nanocatalysts reduce to a Cu/CeO{sub 2} biphase system with significant oxygen vacancies in CeO{sub 2}. Important variations are seen in the Cu particle size and metal dispersion depending on the initial state of the copper oxide-ceria systems. During subsequent in situ oxygen annealing, the Cu precipitated from the CuO/CeO{sub 2} system reoxidized to form CuO through a Cu{sub 2}O intermediate phase as expected. However, the Cu precipitated from the Ce{sub 0.8}Cu{sub 0.2}O{sub 2} solid solution behaved rather differently under oxidizing conditions, and neither oxidized to form CuO nor fully returned to a bulk Ce{sub 0.8}Cu{sub 0.2}O{sub 2} phase in solid solution. We found that {approx} 50% of the Cu returned to a Ce{sub 1-x}Cu{sub x}O{sub 2} solid solution, while the remainder was observed by in situ ETEM to form an amorphous copper oxide phase with a Cu oxidation state similar to Ce{sub 1-x}Cu{sub x}O{sub 2}, but with a local bonding environment similar to CuO. The behavior of the reduced Ce{sub 0.8}Cu{sub 0.2}O{sub 2} reflects strong interactions between Cu and the ceria matrix and illustrates the advantages of working with solid solutions of mixed oxides.

  3. 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.

  4. On the possible involvement of ascorbic acid and copper proteins in leukemia: II. Electron spin resonance (ESR) and atomic absorption investigations on erythrocyte ghosts and plasma.

    PubMed

    Lohmann, W; Greulich, W; Döll, G

    1979-11-01

    The effect of ascorbic acid on white ghosts of erythrocytes and plasma has been investigated by means of ESR spectroscopy. Since the spectra obtained are identical to the one obtained with leukemic blood it is concluded that the receptor for vitamin C has to be searched for in membrane and plasma as well. Determination of Cu and Fe by means of atomic absorption spectroscopy revealed that both of the metals are also present in the membrane. In the case of copper, it must exist there as a protein which has not been identified yet. Oxidizing substances, such as KMnO4, reverse the effect produced by ascorbic acid.

  5. 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.

  6. Photoemission study of YBa(2)Cu(3)O(y) thin films under light illumination.

    PubMed

    Asakura, D; Quilty, J W; Takubo, K; Hirata, S; Mizokawa, T; Muraoka, Y; Hiroi, Z

    2004-12-10

    Heterojunctions of Nb-doped SrTiO3 substrate and YBa(2)Cu(3)O(y) thin films show photoconductivity and photovoltaic effects due to photocarrier injection. Photocarrier injection is expected to be a new carrier doping method in strongly correlated systems instead of chemical substitution. We have studied the nature of photocarrier injection in YBa(2)Cu(3)O(y)/SrTiO(3):Nb using x-ray photoemission spectroscopy with pulsed laser excitation. The core-level spectra shift to higher binding energy by 0.78 eV under pulsed laser illumination at 30 Hz. The energy shift corresponds to the photovoltage, which arises at the interface. In addition, we have observed that the energy shift strongly depends on the frequency of the laser. The lifetime of the injected photoholes has been estimated to be 40 ms by analyzing the frequency dependence.

  7. Molecular dynamics study of the ternary Cu50Ti25Zr25 bulk glass forming alloy

    NASA Astrophysics Data System (ADS)

    Senturk Dalgic, S.; Celtek, M.

    2011-05-01

    The structure and thermodynamic properties of a ternary Cu50Ti25Zr25 metallic glass forming alloy in solid-liquid to glass phases were studied using molecular dynamics (MD) method based on tight-binding (TB) potentials. An atomic description of the melting, glass formation and crystallization process has been analyzed using different heating and cooling rates. The computed Glass Forming Ability (GFA) parameters are in good agreement with experimental data. The structure analysis of the Cu50Ti25Zr25 based on molecular dynamics simulation will be also presented and compared with available MD results. We have also discussed the crystallization transition with two different interatomic potentials used in this work

  8. Heat-treatment studies on thin-film CdS/Cu/x/S solar cells

    NASA Astrophysics Data System (ADS)

    Hmurcik, L.; Serway, R. A.

    1982-12-01

    CdS/CuS polycrystalline solar cells were heat treated in different mixtures of hydrogen and oxygen and examined for the resultant I-V curves. Ten cells were studied, six which were heat treated, then kept in storage for one year. Monitoring was also carried out on the short-circuit current density, the open circuit voltage, the fill factor, and the cell efficiency. Several episodes of heat treatment were performed, with measurements carried out after each. It was determined that changes in the copper-sulfide stoichiometry were the cause of changes in the short-circuit current. Monitoring the changes in the short-circuit current during heating in a hydrogen atmosphere permitted optimization of the cell efficiency to within 5% of its theoretical value. The hydrogen-atmosphere heating is noted to increase the CuS layer stoichiometry.

  9. A new program based on stochastic Liouville equation for the analysis of superhyperfine interaction in CW-ESR spectroscopy

    NASA Astrophysics Data System (ADS)

    Della Lunga, Giovanni; Pezzato, Michela; Baratto, Maria Camilla; Pogni, Rebecca; Basosi, Riccardo

    2003-09-01

    In the slow-motion region, ESR spectra cannot be expressed as a sum of simple Lorentzian lines. Studies of Freed and co-workers, on nitroxides in liquids gained information on the microscopic models of rotational dynamics, relying much on computer programs for simulation of ESR spectra based on the stochastic Liouville equation (SLE). However, application of Freed's method to copper system of biological interest has been for a long time precluded by lack of a full program able to simulate ESR spectra containing more than one hyperfine interaction. Direct extension of the Freed's approach in order to include superhyperfine interaction is not difficult from a theoretical point of view but the resulting algorithm is problematical because it leads to substantial increase in the dimensions of the matrix related to the spin-hamiltonian operator. In this paper preliminary results of a new program, written in C, which includes the superhyperfine interactions are presented. This preliminary version of the program does not take into account a restoring potential, so it can be used only in isotropic diffusion conditions. A comparison with an approximate method previously developed in our laboratory, based on a post-convolution approach, is discussed.

  10. ESR dating pleistocene barnacles from BC and Maine: a new method for tracking sea level change.

    PubMed

    Blackwell, Bonnie A B; Gong, J J J; Skinner, Anne R; Blais-Stevens, Andrée; Nelson, Robert E; Blickstein, Joel I B

    2010-02-01

    Barnacles have never been successfully dated by electron spin resonance (ESR). Living mainly in the intertidal zone, barnacles die when sea level changes cause their permanent exposure. Thus, dating the barnacles dates past sea level changes. From this, we can measure apparent sea level changes that occur due to ocean volume changes, crustal isostasy, and tectonics. ESR can date aragonitic mollusc shells ranging in age from 5 ka to at least 500 ka. By modifying the standard ESR method for molluscs to chemically dissolve 20 microm from off the shells, six barnacle samples from Norridgewock, Maine, and Khyex River, British Columbia, were tested for suitability for ESR dating. Due to Mn2+ interference peaks, the four Maine barnacle samples were not datable by ESR. Two barnacles from BC, which lacked Mn2+ interference, yielded a mean ESR age of 15.1 +/- 1.0 ka. These ages agree well with 14C dates on the barnacles themselves and wood in the overlying glaciomarine sediment. Although stability tests to calculate the mean dating signal lifetime and more ESR calibration tests against other barnacles of known age are needed to ensure the method's accuracy, ESR can indeed date Balanus, and thus, sea level changes.

  11. Raman studies of laser-written patterns in YBa2Cu3Ox films

    NASA Astrophysics Data System (ADS)

    Li, Y. B.; Shelley, C.; Cohen, L. F.; Caplin, A. D.; Stradling, R. A.; Kula, W.; Sobolewski, Roman; MacManus-Driscoll, J. L.

    1996-09-01

    Patterns on YBa2Cu3O6.87 films, laser written in O2 or N2 atmospheres, and with various writing power densities and scanning speeds, have been studied by Raman scattering. For laser writing in O2 at atmospheric pressure, with low power density and fast scanning speed, it is found systematically that the oxygen content of YBa2Cu3Ox can be reduced. Only when the writing power density is high and the scanning speed is low (e.g., 2.3 mW/μm2 and 1 μm/s), do the laser-irradiated lines in an O2 atmosphere approach full oxygenation (x→7). For laser writing in N2 at atmospheric pressure, the oxygen stoichiometry always decreases, rendering the lines nonsuperconducting. The structural phase transition from orthorhombic to tetragonal can be identified with laser writing in a N2 atmosphere with a writing power density of 1.9 mW/μm2 and a scanning speed of 20 μm/s. The oxygen O(4) line (˜500 cm-1) and the Ba line (115 cm-1) disappear, and the intensity of the Cu(2) line (144 cm-1) rises sharply when the phase transition occurs. This study shows how Raman scattering can be used as a routine technique, which is fast, sensitive, and nondestructive, and is able to measure oxygen content on a fine scale (a few μm) during high-Tc superconductor device processing.

  12. 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.

  13. 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.

  14. 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.

  15. Martensitic transformation in a Cu-Zn-Al alloy studied by 63Cu and 27Al NMR

    NASA Astrophysics Data System (ADS)

    Rubini, S.; Dimitropoulos, C.; Gotthardt, R.; Borsa, F.

    1991-08-01

    27Al and 63Cu line shape, Knight shift, and relaxation rates over a wide range of temperature and external magnetic field are reported for a Cu-Zn-Al alloy displaying a martensitic phase transformation (MPT) at MS=152 K. Changes in line shape, linewidth, and T-12 at the MPT are detected for both nuclei, and are found to be consistent with the local atomic rearrangement occurring at the transformation. A double structure for the 27Al NMR line is observed in a small range of temperature below MS, and interpreted as the superposition of the signals arising from the two coexisting phases. It is shown that the growth of the martensitic phase during the cooling can be monitored by means of the deconvolution of the 27Al spectrum into the two components. From the analysis, it is inferred that a sudden formation of extensive regions in the martensitic phase occurs at the transition. The Knight shift and the Korringa term (T1T)-1 are slightly different in the two phases, indicating a small increase of the density of s electrons at the Fermi surface at the nuclear sites. The enhancement factors of the susceptibility and of the spin-lattice relaxation rate do not seem to be affected by the MPT but are different when measured at the Al or Cu site, indicating a local nonuniform charge-density distribution in the unit cell. A small enhancement of T-11 is observed for both nuclei in the temperature interval in which the growth of the martensite within the austenite is detected. The anomalous contribution to the relaxation is interpreted as due to strong local charge-density fluctuations caused by atomic motion at the interfaces between the two phases. No precursor effects were detected on the NMR parameters above MS, indicating the absence of a static or long-lived microstructure of the product phase and of a static short-wavelength modulation of the lattice.

  16. 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.

  17. EPR study of Cu(2+) ion doped orotato(nicotinamid)cobalt(II) single crystal.

    PubMed

    Yıldırım, I; Karabulut, B; Büyükgüngör, O

    2016-01-05

    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.

  18. Scanning tunneling microscopy studies of graphene and hydrogenated graphene on Cu(111)

    NASA Astrophysics Data System (ADS)

    Hollen, Shawna M.; Gambrel, Grady; Tjung, Steven; Santagata, Nancy M.; Johnston-Halperin, Ezekiel; Gupta, Jay A.

    2015-03-01

    Because of the innate sensitivity of 2D material surfaces, it is increasingly important to understand and characterize surface functionalization and interactions with environmental elements, such as substrate, metallic contacts, and adatoms. We developed a method for reproducible, epitaxial growth of pristine graphene islands on Cu(111) in UHV and use scanning tunneling microscopy and spectroscopy (STM) to study the interaction of these graphene islands with the Cu substrate. Tunneling spectroscopy measurements of the electronic surface states over the graphene islands indicate a lower local work function, decreased coupling to bulk Cu states, and a decreased electron effective mass. Additionally, we developed a novel field electron dissociation technique to form hydrogen-terminated graphene at low temperatures and in UHV. This method produced what may be the first STM images of crystalline hydrogenated graphene. The pristine graphene island is then recovered by scanning at a high tip-sample bias. The hydrogenation and its reversibility suggest writing lateral 2D devices using the STM tip. Toward this end, we are developing the capability to repeat the hydrogenation on working graphene devices. This research is supported by the Center for Emergent Materials NSF-funded MRSEC (DMR-0820414)

  19. Surface reconstruction modes of Cu 2O(001) surface: A first principles study

    NASA Astrophysics Data System (ADS)

    Islam, Mazharul M.; Diawara, Boubakar; Maurice, Vincent; Marcus, Philippe

    2010-08-01

    The stabilization mechanism of the polar, copper terminated Cu 2O(001) surface by means of complex surface reconstruction was studied theoretically with a combination of static and molecular dynamics calculations. The experimentally reported "3√2 × 1" surface structure was constructed and characterized for the first time. The combination of simulated annealing with molecular dynamics shows that Cu +-Cu + dimers are formed in the first layer along the equivalent [011] and [01-1] directions at elevated temperature. There is a relaxation of the atoms that separates copper cations from nearest neighbor rows. Using the experimentally observed superstructure cell allows decoupling the symmetry equivalent dimers. The structural reconstructions were characterized by the electronic properties calculations. It is observed that the dimers are formed due to the d-d interaction of the copper atoms. Finally, the symmetry driven reconstructed structure was investigated by DFT STM. The simulated STM images show that copper atoms have higher density than oxygen atoms at the surface and produce the positive surface corrugation.

  20. Incommensurate modulated structure study of a Cu-Zn-Al-Zr phase

    SciTech Connect

    Chung, C.Y.; Zou, W.H.; Han, X.D.; Lam, C.W.H.; Lai, J.K.L.; Gao, M.; Duan, X.F.

    1998-09-18

    Zr was added to Cu-Zn-Al shape memory alloy as a grain refinement element. There are two new phases, Cu{sub 50.2}Zr{sub 24.6}Al{sub 17.3}Zn{sub 7.9} (at%) (Z{sub 1} phase) and Cu{sub 57.4}Zr{sub 20.4}Zn{sub 10.3}Al{sub 11.9} (at%) (Z{sub 2}) phase is studied in detail in the present paper. The results of electron diffraction and high-resolution electron microscopy (HREM) investigations indicated a one-dimensional incommensurate modulated structure in the Z{sub 2} phase. The average structure of the phase is base-centered orthorhombic. The systematic reflection conditions associated with the main and satellite reflections demonstrate that the Bravais class of the Z{sub 2} phases is P{sub 11{bar 1}}{sup Cmmm} type in a (3 + 1) dimensional space for the incommensurate modulated structure. The substitution modulation effects of the Al and Zr elements are revealed by energy-filtered transmission electron microscopy (EFTEM), {l_brace}1{bar 3}{bar 2}{r_brace} compound-type twins are observed in the Z{sub 2} phase. The relationship between the Z{sub 1} and Z{sub 2} phases in the alloy is discussed.

  1. 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.

  2. 25(OH) vitamin D serum values and rheumatoid arthritis disease activity (DA S28 ESR)

    PubMed Central

    Sahebari, Maryam; Mirfeizi, Zahra; Rezaieyazdi, Zahra; Rafatpanah, Houshang; Goshyeshi, Ladan

    2014-01-01

    Background: The role of vitamin D in the pathogenesis of rheumatoid arthritis is under investigation. This study was designed to evaluate the correlation between serum values of 25(OH) vitamin D [25(OH)D] and disease activity in rheumatoid arthritis (RA) patients according to Disease Activity Score 28 joints and ESR (DA S28 ESR). Methods: Ninety-nine patients according to ACR classification criteria for RA and 68 healthy controls were included in this study. The participants with known confounding risk factors affecting serum values of 25(OH)D were excluded. All patients were under treatment with supplementary calcium carbonate (1500mg), 25(OH)D (800U), and Hydroxychloroquine (6mg/kg). The control group was mostly recruited from patients’ relatives who lived with them to minimize the impact of diverse lifestyles on 25(OH)D status. Disease activity was assessed by DA S28 ESR. Serum concentrations of 25(OH)D were measured. Serum values of 25(OH)D less than 50 nmol/L were considered 25(OH)D deficiency. Results: The mean 25(OH)D serum values were 83.74±46.45 nmol/L in patients and 46.53±34.07 nmol/L in controls. After adjustment for age, sex and BMI, multivariate analysis showed no correlation between 25(OH)D serum levels and DAS in RA (P=0.29, rp=0.11). However, 25(OH)D serum values were significantly lower in patients with early diagnosed RA compared with the other patients (p=0.012). In the early diagnosed patients, 25(OH)D and anti-CCP serum values were negatively correlated (P=0.04, rs=-0.5). Conclusion: This study showed that there was no correlation between 25(OH)D serum values and DAS over a short duration of disease course. However, in early RA, 25(OH) D serum values were lower than the established RA. PMID:25202442

  3. Structural, magnetic, DC-AC electrical conductivities and thermo electric studies of MgCuZn Ferrites for microinductor applications.

    PubMed

    Varalaxmi, N; Sivakumar, K V

    2013-01-01

    Multilayer chip inductors (MLCIs) have been rapidly developed for electromagnetic applications. NiCuZn ferrites are the most preferred ferrite materials to produce MLCIs. MgCuZn ferrites have similar properties to those of NiCuZn ferrites. MgCuZn ferrites owing to their superior properties like low magnetostriction, environmental stability, low stress sensitivity, high resistivity and low cost can replace NiCuZn ferrites, which have a wide range of electronic applications. In view of this, a series of polycrystalline MgCuZn ferrites with generic formula MgxCu0.5Zn0.5-xFe2O4 (X=0.0 0.1, 0.2, 0.3, 0.4 and 0.5) are successfully synthesized by conventional double sintering technique. The samples were then characterized by the X-ray diffraction patterns (XRD) microstructural studies and the grain size was estimated using SEM micrographs. The sintered ferrites have been investigated in their magnetic, electrical and thermoelectric effect studies, which were carried out in the temperature range from 30 °C to 490 °C. The investigated ferrites are found to exhibit excellent properties that are suitable for the core materials in multilayer chip inductors, and the results are discussed.

  4. Cu(Nor)2·5H2O, a complex of Cu(II) with Norfloxacin: theoretic approach and biological studies. Cytotoxicity and genotoxicity in cell cultures.

    PubMed

    Di Virgilio, A L; León, I E; Franca, C A; Henao, I; Tobón, G; Etcheverry, S B

    2013-04-01

    Norfloxacin is a fluoroquinolone antibiotic used in the treatment of bacterial infections. In this article, we studied the potential antitumoral action of a complex of Norfloxacin with Cu(II), Cu(Nor)(2)·5H(2)O on osteosarcoma cells (UMR106) and calvaria-derived cells (MC3T3-E1), evaluating its cytotoxicity and genitoxicity. We have also elucidated the more stable conformation of this complex under physiologic conditions by Molecular Dynamic simulations based on the model of the canonical ensemble and PM6 force field. When solvent effect was taken into account, the complex conformation with both carbonyl groups in opposite sides displayed lower energy. Cu(Nor)(2)·5H(2)O caused an inhibitory effect on the proliferation on both cell lines from 300 μM (P < 0.01). Nevertheless, the decline on cell proliferation of UMR106 cells was more pronounced (45 % vs basal) than in MC3T3-E1 cells (20 % vs basal) at 300 μM (P < 0.01). Cu(Nor)(2)·5H(2)O altered lysosomal metabolism (Neutral Red assay) in a dose-dependent manner from 300 μM (P < 0.001). Morphological studies showed important transformations that correlated with a decrease in the number of cells in a dose-dependent manner. Moreover, Cu(Nor)(2)·5H(2)O caused statistically significant genotoxic effects on both osteoblast cell lines in a lower range of concentrations (Micronucleus assay) (P < 0.05 at 10 μM, P < 0.001 from 25 to 50 μM). UMR106 cells displayed a dose-related genotoxic effect between 5 and 25 μM while the MC3T3-E1 cells showed a narrower concentration dependent range. Altogether, these results suggest that Cu(Nor)(2)·5H(2)O is a good candidate to be further evaluated for alternative therapeutics in cancer treatment.

  5. Single Crystal EPR and Optical Studies of Cu(II) Doped Zinc Ammonium Phosphate Hexahydrate: A Case of Rhombic Distortion

    NASA Astrophysics Data System (ADS)

    Poonguzhali, E.; Srinivasan, R.; Ravikumar, R. V. S. S. N.; Ravikumar, R. V. S. S. N.; Chandrasekhar, A. V.; Reddy, B. J.; Reddy, Y. P.; Sambasiva Rao, P.

    Single crystal EPR and optical studies of Cu(II) doped ZnNH4PO4·6H2O (Zinc struvite) have been carried out at room and liquid nitrogen temperatures. The g and A tensors indicate that the impurity has entered the lattice substitutionally. Even though the coordination polyhedron around the host Zn(II) is a compressed octahedron of oxygen atoms of water, the Cu(II) ion has an elongated octahedron corresponding to dx2-y2 ground state. The optical spectrum shows four bands at 1205, 1095, 833 and 805nm, which confirms the octahedral coordination of Cu(II) with rhombic (C2V) distortion.

  6. Amine-based extraction recovery of Cu(II) from aqueous solutions in the presence of EDTA. Equilibrium studies

    SciTech Connect

    Juang, R.S.; Chen, Y.J.; Huang, I.P.

    1999-11-01

    The distribution ratios of Cu(II) between kerosene solutions of Aliquat 336 and water containing EDTA (ethylenediaminetetraacetic acid) are measured. Experiments were performed as a function of the pH, the concentration of Cu(II), the concentration ratio of EDTA to Cu(II), and the concentration of amine. It is shown that the distribution ratios first increase with pH and then decrease with further increase in pH up to 7.0. The effect of temperature on the extraction was studied, and the enthalpy of the extraction reaction was determined. Finally, the nonideal behavior of the organic phase is discussed.

  7. [Synthesis and Spectroscopic Study of a Chemosensor for Naked Eye Recognition of Cu2+ and Hg2+].

    PubMed

    Cao, Li; Qian, Ya-ao; Huang, Yan; Cao, Juan; Jia, Chun-man; Liu, Chun-ling; Zhang, Qi; Lu, Zheng-rong

    2015-07-01

    Compound L, as the procedural sensor for the detection of Cu2+ and Hg2+, was designed and synthesized based on the coumarin-modified rhodamine derivative. The structure of compound L was characterized by NMR, high resolution mass spectrometry and infrared method. Its sensing behavior toward various metal ions was investigated with absorbance methods. The study found that L had good selectivity and sensitivity for Cu2+. When addition of various metal ions (Zn2+, Hg2+, Cu2+, Fe3+, Cd2+, CO2+, Ni2+, Mg2+, Ca2+, Al3+, La3+, K+, Na+, Mn2+, Pb2+ and Ag+), only Cu2+ could induce a visible change of solution from colourless to pink and a new absorption band centered at 534 nm appear, which indicated that compound L could be used for the naked eye detection of Cu2+. From UV titration, the detection limit was about 1.9 X 10(-8) mol x L(-1). Test strips based on L were fabricated, and this test strips could act as a convenient and efficient Cu2+ test kit. The binding ratio of the complex of L-Cu2+ was 1:1 according to the Job's plot and high resolution mass spectrometer (HRMS) experiments. Moreover, Upon addition of 1 equiv. EDTA to the mixture of L and Cu2+ in DMSO solution, colour changed from pink to almost colourless, indicating that the EDTA replaced the receptor L to coordinate with Cu2+. Therefore, L could be classified as a reversible sensor for Cu2+. In addition, when adding Hg2+ to L-Cu2+ complexes, a visible change of solution from pink to colourless was observed, while other metal ions didn't cause this change. Thus, L-Cu2+ complex also could be used for the naked eye recognition of Hg2+, and the detection limit was calculated about 2.9 x 10(-1) mol x L(-1) according to the UV titration. Consequently, this procedural sensor L could be use for the orderly naked eye recognition of Cu2+ and Hg2+.

  8. A study of high copper amalgams. IV. Formation of eta Cu-Sn (Cu6Sn5) crystals in a high copper dispersant amalgam matrix.

    PubMed

    Okabe, T; Mitchell, R J; Fairhurst, C W

    1979-03-01

    In an HCD amalgam, eta Cu-Sn crystals were found dispersed within gamma1 matrix areas. Previously, eta Cu-Sn phase was thought to form only as part of a reaction zone surrounding Ag-Cu dispersant particles. The eta Cu-Sn crystals found in matrix areas of this HCD amalgam are smaller and more widely scattered than eta Cu-Sn crystals dispersed in the gamma1 matrix of HCSC amalgams.

  9. 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.

  10. 63Cu nuclear magnetic resonance study of Pr(1.85)Ce(0.15)Cu(1-x)Ni(x)O(4): Ni-induced spin density oscillation and modification of the low energy spin fluctuations.

    PubMed

    Williams, G V M; Jurkutat, M; Rybicki, D; Haase, J

    2011-02-23

    We report the results from a (63)Cu nuclear magnetic resonance (NMR) study of the electron-doped high temperature superconducting cuprate (HTSC) Pr(1.85)Ce(0.15)Cu(1-x)Ni(x)O(4). We find that Ni induces a magnetic broadening of the (63)Cu NMR spectra that can be interpreted in terms of an induced spin density oscillation about the Ni site, similar to that reported from (63)Cu NMR measurements on the hole-doped HTSCs when Zn is partially substituted for Cu. There is also an additional temperature-dependent contribution to the (63)Cu spin-lattice relaxation rate that can be interpreted in terms of an Ni-induced modification of the low energy spin fluctuations. Furthermore, the spin fluctuations are intrinsically spatially inhomogeneous and additional inhomogeneities are induced by Ni.

  11. Cu nuclear magnetic resonance study of charge and spin stripe order in La1.875Ba0.125CuO4

    NASA Astrophysics Data System (ADS)

    Pelc, D.; Grafe, H.-J.; Gu, G. D.; Požek, M.

    2017-02-01

    We present a Cu nuclear magnetic/quadrupole resonance study of the charge stripe ordered phase of LBCO, with detection of previously unobserved ("wiped-out") signal. We show that spin-spin and spin-lattice relaxation rates are strongly enhanced in the charge ordered phase, explaining the apparent signal decrease in earlier investigations. The enhancement is caused by magnetic, rather than charge fluctuations, conclusively confirming the long-suspected assumption that spin fluctuations are responsible for the wipeout effect. Observation of the full Cu signal enables insight into the spin and charge dynamics of the stripe-ordered phase, and measurements in external magnetic fields provide information on the nature and suppression of spin fluctuations associated with charge order. We find glassy spin dynamics, in agreement with previous work, and incommensurate static charge order with charge modulation amplitude similar to other cuprate compounds, suggesting that the amplitude of charge stripes is universal in the cuprates.

  12. 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.

  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.

  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. ESR and TL mechanism in CaSO4 : Ag co-doped phosphors

    NASA Astrophysics Data System (ADS)

    Dhabekar, Bhushan; Menon, Sanjeev; Alagu Raja, E.; Sanaye, S. S.; Gundu Rao, T. K.; Bhatt, B. C.; Kher, R. K.

    2006-06-01

    Thermoluminescence (TL) studies have been carried out on CaSO4 : Mn, CaSO4 : Ag,Mn, CaSO4 : Ag,Nd, CaSO4 : Ag,Mn,Nd, CaSO4 : Ag,Zr and CaSO4 : Ag,Mn,Zr phosphors. It is found that TL at 360 °C in CaSO4 : Ag,Mn,Nd is about 40 times that of CaSO4 : Ag,Mn and about 170 times that of CaSO4 : Ag,Nd. This shows that the presence of an efficient luminescent centre (Mn2+) as well as a trivalent impurity (such as Nd3+ or Y3+) is important for enhancement of TL at 360 °C in the CaSO4 : Ag,Mn,Nd phosphor system. Electron spin resonance (ESR) studies show that the peak at 360 °C correlates with an Ag2+ centre formed due to γ-irradiation and observable only below -170 °C. The Ag2+ centre is characterized by an axial g-tensor with principal values g|| = 2.38 and gbottom = 2.41. ESR studies further indicate that the precursor to a centre observable at low temperature (-170 °C) appears to act as the recombination centre for the TL peak at 360 °C. The low temperature centre is characterized by the g-values g|| = 2.0023 and gbottom = 2.0038 and is assigned to the SO_{3}^{ - } radical.

  16. EBSD Investigation of Cu-Sn IMC Microstructural Evolution in Cu/Sn-Ag/Cu Microbumps During Isothermal Annealing

    NASA Astrophysics Data System (ADS)

    Wang, S. J.; Hsu, L. H.; Wang, N. K.; Ho, C. E.

    2014-01-01

    The microstructural evolution of Cu/Sn-Ag (~5 μm)/Cu Cu-bump-on-line (CuBOL) joints during isothermal annealing at 180°C was examined using a field-emission scanning electron microscope equipped with an electron backscatter diffraction (EBSD) system. Cu6Sn5 and Cu3Sn were the two key intermetallic compound (IMC) species that appeared in the CuBOL joints. After annealing for 24 h (= t), the solder had completely converted to Cu-Sn IMCs, forming an "IMC" joint with Cu/Cu3Sn/Cu6Sn5/Cu3Sn/Cu structure. EBSD analyses indicated that the preferred orientation of the hexagonal Cu6Sn5 (η) was , while the preferred orientation was (100) for the monoclinic Cu6Sn5 structure (η'). Upon increasing t to 72 h, Cu6Sn5 entirely transformed into Cu3Sn, and the IMC joint became Cu/Cu3Sn/Cu accordingly. Interestingly, the grain size and crystallographic orientation of Cu3Sn displayed location dependence. Detailed EBSD analyses in combination with transmission electron microscopy on Cu3Sn were performed in the present study. This research offers better understanding of crystallographic details, including crystal structure, grain size, and orientation, for Cu6Sn5 and Cu3Sn in CuBOL joints after various annealing times.

  17. Organ dose conversions from ESR measurements using tooth enamel of atomic bomb survivors.

    PubMed

    Takahashi, Fumiaki; Sato, Kaoru

    2012-03-01

    Dose conversions were studied for dosimetry of atomic bomb survivors based upon electron spin resonance (ESR) measurements of tooth enamel. Previously analysed data had clarified that the tooth enamel dose could be much larger than other organ doses from a low-energy photon exposure. The radiation doses to other organs or whole-body doses, however, are assumed to be near the tooth enamel dose for photon energies which are dominant in the leakage spectrum of the Hiroshima atomic bomb assumed in DS02. In addition, the thyroid can be a candidate for a surrogate organ in cases where the tooth enamel dose is not available in organ dosimetry. This paper also suggests the application of new Japanese voxel phantoms to derive tooth enamel doses by numerical analyses.

  18. Post-shock chemical and ESR analysis of acrylamide and selected anthracene derivatives. [9-cyanoanthracene

    SciTech Connect

    Dodson, B.W.; Arnold, C. Jr.; Venturini, E.L.; Lenahan, P.M.

    1983-01-01

    We report on a series of impact recovery experiments performed on organic samples. Acrylamide was loaded to peak stresses of 4.8 and 6.7 GPa in a copper capsule using an air-driven projectile. No polyacrylamide was formed in these impact experiments. ESR studies reveal approx. 1 ppM free radicals, which are stable in the acrylamide lattice. Upon solution in tetrahydrofuran (THF), these radicals become mobile, resulting in polymer formation, a reaction not seen in unshocked acrylamide and 9-cyanoanthracene (9-CA) in the stress range 1.8 to 4.0 GPa. The residual radical density in the 9-CA was roughly 10 times that in the anthracene. A systematic relation between peak stress and formation of specific radicals were observed. 3 figures.

  19. A theoretical study of surfactant action in the layer-by-layer homoepitaxial growth of metals: the case of In on Cu(111)

    NASA Astrophysics Data System (ADS)

    Jiang, Ming; Qiu, Min; Zhao, Yu-Jun; Cao, Pei-Lin

    1998-02-01

    A surfactant-mediated homoepitaxial metal system, Cu/In/Cu(111), is studied by using first-principles calculations and the kinetic Monte Carlo method. A new repulsion model is proposed for the Cu/In/Cu(111) system where surface-substitutional In atoms repel diffusing Cu adatoms and build a repulsion network. This repulsion network results in an average increase of terrace barriers for adatoms Cu and enhanced island density. The layer-by-layer growth for the Cu/In/Cu(111) system is achieved with a repulsion model in a kinetic Monte Carlo simulation. The importance of the additional barrier ΔE is confirmed in determining film morphology.

  20. Comparative study of alumina-supported CuO and CuCr/sub 2/O/sub 4/ as catalysts for CO oxidation

    SciTech Connect

    Severino, F.; Brito, J.; Carias, O.; Laine, J.

    1986-11-01

    Alumina-supported CuO and CuCr/sub 2/O/sub 4/ catalysts of various compositions were prepared and their activity for CO oxidation measured. Fresh, pretreated with CO, and reoxidized catalysts were studied. In general, the activity increased with the CO pretreatment. The extent of the activation depended on the catalyst composition. Thus, copper catalysts were more active than copper chromite at low metal concentrations (< 12 wt%), but the opposite was observed at concentrations higher than about 12 wt%. The results on activity behavior, together with TPR and XRD spectra, suggest that the active species are related to copper cations. In the low concentration copper catalysts, the most active surface is generated after CO pretreatment, followed by a fast reoxidation occurring at the first stages of the reaction. In the high concentration copper catalysts, the CO pretreatment produced an induction period as a result of excessive reduction. It is suggested that the role of chromium is to limit the extent of reduction through the formation of the CuCr/sub 2/O/sub 4/ phase. The presence of this phase also resulted in catalysts less prone to deactivation, as compared to copper on alumina catalysts.

  1. The formation of the reacted interface for the Si/Cu/Pd system: An ultraviolet photoemission study

    NASA Astrophysics Data System (ADS)

    Abbati, I.; Carbone, C.; Ciucci, G.; Michelis, B. De; Fasana, A.; Mondini, R.

    1983-12-01

    Various coverage of Pd were deposited on substrates formed by few layers of Cu on Si (111) face at room temperature. Photoemission results show that the formation of Pd 2 Si-like compound is strongly inhibited by the presence of the Cu/Si interlayer and suggest that for the studied system the heat of formation of the compound is not the only parameter that controls the thickness of the intermixed region.

  2. Comparative studies of glow peaks and kinetic trapping parameters of LiF(Mg,Cu), LiF(Mg,Cu,P), LiF(Mg,Cu,Si) and LiF(Mg,Cu,Na,Si) single crystals

    NASA Astrophysics Data System (ADS)

    Laopaiboon, R.; Bootjomchai, C.; Pencharee, S.; Laopaiboon, J.

    2014-02-01

    Glow curve structure and kinetic trapping parameter of the thermoluminescent (TL) phosphors based on LiF(Mg,Cu) LiF(Mg,Cu,P) LiF(Mg,Cu,Si) and LiF(Mg,Cu,Na,Si) single crystals were investigated (denoted as SMC, SMCP, SMCS and SMCNS, respectively). Wet mixing and drying before TL phosphors production in single-crystal form were achieved by the Bridgeman method. The transparent solid single crystals were cut to the size of 5.0×5.0×0.6 mm3 for use as thermoluminescence dosimeters (TLD). Four different types of TLD were irradiated with X-ray photon energy 128 keV in the dose of 3 mGy after dual step pre-irradiation annealing. From the glow curve structure, the geometrical factors (μ) were calculated. The graph created by Chen confirms the first-order kinetics. Moreover, the glow curve shape results in more fading of the TLD 100 sample than the SMCS and SMCNS samples. It is evident that the kinetic trapping parameters depend on the type of dopant. The frequency factors of all TLD single crystals are higher than TLD100 (poly-crystal). These results are useful to provide the TL trapping and recombination centers for these materials.

  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.

  4. Experimental study of enhanced heat transfer by addition of CuO nanoparticle

    NASA Astrophysics Data System (ADS)

    Jesumathy, Stella; Udayakumar, M.; Suresh, S.

    2012-06-01

    An energy storage system has been designed to study the thermal characteristics of paraffin wax with an embedded nano size copper oxide (CuO) particle. This paper presents studies conducted on phase transition times, heat fraction as well as heat transfer characteristics of paraffin wax as phase change material (PCM) embedded with CuO nanoparticles. 40 nm mean size CuO particles of 2, 5 and 10% by weight were dispersed in PCM for this study. Experiments were performed on a heat exchanger with 1.5-10 l/min of heat transfer fluid (HTF) flow. Time-based variations of the temperature distributions are revealed from the results of observations of melting and solidification curves. The results strongly suggested that the thermal conductivity enhances 6, 6.7 and 7.8% in liquid state and in dynamic viscosity it enhances by 5, 14 and 30% with increasing mass fraction of the CNEPs. The thermal conductivity ratio of the composites can be augmented by a factor up to 1.3. The heat transfer coefficient during solidification increased about 78% for the maximum flow rate. The analysis of experimental results reveals that the addition of copper oxide nanoparticles to the paraffin wax enhances both the conduction and natural convection very effectively in composites and in paraffin wax. The paraffin wax-based composites have great potential for energy storage applications like industrial waste heat recovery, solar thermal applications and solar based dynamic space power generation with optimal fraction of copper oxide nanoparticles.

  5. Surface and interface study of Cu (film)/SiC (substrate) system

    NASA Astrophysics Data System (ADS)

    An, Z.; Hirai, M.; Kusaka, M.; Iwami, M.

    2003-06-01

    We have investigated the diffusion, agglomeration, and reaction at Cu/3C-SiC interface, using soft X-ray emission spectroscopy (SXES) and photoemission electron microscopy (PEEM). By measuring Si Kβ emission, the diffusion and/or agglomeration of Cu atoms at Cu (60 nm)/3C-SiC interface were found to occur obviously after annealing at 350 °C and to be enhanced with increasing annealing temperature. PEEM observations for a Cu (30 nm)/3C-SiC sample indicated that the Cu film began agglomerating at 550 °C annealing from the edge of the Cu film on the 3C-SiC substrate. The agglomeration spread from the edge to the middle region of the Cu film with the increase of temperature. At 850 °C annealing, the Cu agglomeration was observed in the whole area of the Cu film. The formation of Cu 3Si was found from SXES analysis for Cu/3C-SiC(0 0 1) specimens annealed at temperatures higher than ˜850 °C, which indicates the agglomerated material observed by PEEM at 850 °C is Cu 3Si.

  6. An ESR study of the UV degradation of FEP

    NASA Technical Reports Server (NTRS)

    George, G. A.; Hill, D. J. T.; Odonnell, J. H.; Pomery, P. J.; Rasoul, F.

    1992-01-01

    Spacecraft in low earth orbit are subjected to significant levels of high energy radiation, including ultraviolet (UV) and visible ultraviolet (VUV) wavelengths. The effects of UV radiation are enhanced over those at the surface of the earth, where the only incident wavelengths are greater than 290 nm. In low earth orbit the incident UV wavelengths extend below 290 nm into the VUV region, where the Lyman alpha-emissions of atomic hydrogen occur at 121 nm. In addition to electromagnetic radiation, in low earth orbit polymer materials may also be subjected to atomic oxygen particle radiation, which will result in direct oxidation of the polymer.

  7. A study on the inhibition kinetics of bioaccumulation of Cu(II) and Ni(II) ions using Rhizopus delemar.

    PubMed

    Açikel, Unsal; Alp, Tuğba

    2009-09-15

    The microbial growth and simultaneous bioaccumulation of Cu(II) and Ni(II) ions during the growth of Rhizopus delemar in molasses medium was investigated in a batch system. The level of Cu(II) and Ni(II) bioaccumulation and microbial growth was dependent on pH, molasses sucrose concentration and initial Cu(II) and Ni(II) ion concentrations. An increase in initial total metal ion concentration inhibited both the growth rate of fungus and the bioaccumulation capacity. Lineweaver-Burk plot of Monod equation was used to study the inhibition kinetics of bioaccumulation of Cu(II) and Ni(II) and the intrinsic and apparent model parameters were evaluated in metals-free and metals-contaminated fermentation media. The maximum specific growth rate (micro(m)) and the Monod constant (K(s)) of microorganism in metals-free media were found as 0.405 L/h and 3.977 g/L, respectively. As micro(m) remained constant in the presence of increasing concentrations of Cu(II) and Ni(II) ions, the combined inhibition of Cu(II) and Ni(II) ions on the growth rate of R. delemar was found to be a competitive inhibition. The inhibition constants for Cu(II) and Ni(II) ions were determined as 56.71 mg Cu(II)/L and 47.44 mg Ni(II)/L. As the bioaccumulation of Cu(II) and Ni(II) ions was reduced by the presence of increasing concentrations of the other metal ion, compared with the single-metal systems, the individual action of Cu(II) and Ni(II) ions on the bioaccumulation of R. delemar was generally found to be antagonistic. On the other hand, the total combined effects of Cu(II) and Ni(II) ions on the bioaccumulation of R. delemar are thought to be synergistic since the total bioaccumulated metal ion quantities per unit mass of biomass were higher than those obtained in the growth media containing Cu(II) and Ni(II) ions alone at the same concentrations.

  8. 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.

  9. Ionized physical vapor deposition of Cu on 300 mm wafers: A modeling study

    NASA Astrophysics Data System (ADS)

    Rauf, Shahid; Ventzek, Peter L. G.; Arunachalam, Valli

    2001-03-01

    A two-dimensional model has been used to understand the physics and process engineering issues associated with a conceptual 300 mm Cu internal-coil ionized physical vapor deposition reactor. It has been found that inductive coupling from the coil is the primary source of plasma production. Since the coil is in direct contact with the plasma, a significant fraction of the coil power is deposited in the gas capacitively as well. This results in sputtering of the Cu coil, which tends to improve Cu flux uniformity at the outer edges of the wafer. Since the Cu ionization threshold is much lower than Ar, Cu+ density is comparable to Ar+ density even though ground state Cu density is much smaller than Ar. Significant fraction of the neutral Cu flux to the wafer is in the metastable or athermal state. The effects of several actuators, reactor dimensions, and buffer gas on important plasma and process quantities have also been investigated. Electron density in the reactor and Cu ionization fraction increases with increasing total coil power because of enhanced ionization. Total coil power however does not affect the Cu density appreciably, except near the coil where enhanced coil sputtering increases the Cu density. Decrease in dc target voltage with increasing coil power decreases Cu+ loss to the target and results in an increase in total Cu flux to the wafer. Electron and Cu density in the reactor increase with increasing dc target power. This is due to enhancement in target sputtering and consequent ionization of the sputtered Cu. While this increases the total Cu flux to the wafer, ionization fraction is not affected much. It is demonstrated that uniformity of Cu flux to the wafer and ionization fraction can be controlled by means of the terminating capacitor at the coil. Decreasing the terminating capacitance increases the coil voltage, enhances coil sputtering and enhances Cu flux toward the outer edges of the wafer. This, however, decreases the amount of power that

  10. ESR1 and PGR polymorphisms are associated with estrogen and progesterone receptor expression in breast tumors.

    PubMed

    Hertz, Daniel L; Henry, N Lynn; Kidwell, Kelley M; Thomas, Dafydd; Goddard, Audrey; Azzouz, Faouzi; Speth, Kelly; Li, Lang; Banerjee, Mousumi; Thibert, Jacklyn N; Kleer, Celina G; Stearns, Vered; Hayes, Daniel F; Skaar, Todd C; Rae, James M

    2016-09-01

    Hormone receptor-positive (HR+) breast cancers express the estrogen (ERα) and/or progesterone (PgR) receptors. Inherited single nucleotide polymorphisms (SNPs) in ESR1, the gene encoding ERα, have been reported to predict tamoxifen effectiveness. We hypothesized that these associations could be attributed to altered tumor gene/protein expression of ESR1/ERα and that SNPs in the PGR gene predict tumor PGR/PgR expression. Formalin-fixed paraffin-embedded breast cancer tumor specimens were analyzed for ESR1 and PGR gene transcript expression by the reverse transcription polymerase chain reaction based Oncotype DX assay and for ERα and PgR protein expression by immunohistochemistry (IHC) and an automated quantitative immunofluorescence assay (AQUA). Germline genotypes for SNPs in ESR1 (n = 41) and PGR (n = 8) were determined by allele-specific TaqMan assays. One SNP in ESR1 (rs9322336) was significantly associated with ESR1 gene transcript expression (P = 0.006) but not ERα protein expression (P > 0.05). A PGR SNP (rs518162) was associated with decreased PGR gene transcript expression (P = 0.003) and PgR protein expression measured by IHC (P = 0.016), but not AQUA (P = 0.054). There were modest, but statistically significant correlations between gene and protein expression for ESR1/ERα and PGR/PgR and for protein expression measured by IHC and AQUA (Pearson correlation = 0.32-0.64, all P < 0.001). Inherited ESR1 and PGR genotypes may affect tumor ESR1/ERα and PGR/PgR expression, respectively, which are moderately correlated. This work supports further research into germline predictors of tumor characteristics and treatment effectiveness, which may someday inform selection of hormonal treatments for patients with HR+ breast cancer.

  11. Composition of α- F e nanoparticles precipitated from CuFe alloy studied by hyperfine interactions

    NASA Astrophysics Data System (ADS)

    Kubániová, Denisa; Cesnek, Martin; Milkovi c, Ondrej; Kohout, Jaroslav; Miglierini, Marcel

    2016-12-01

    Iron-based nanoparticles prepared by precipitation from solid solution of saturated binary Cu-Fe alloy were studied by transmission electron microscopy, high-energy X-ray diffraction and Mössbauer spectroscopy. The results showed that the investigated as-prepared nanoparticles contained two phases. The major phase was determined as α- F e and the minor phase as γ- F e 2 O 3. Furthermore, additionally annealed samples in Ar protective atmosphere were investigated. Results showed clear decrease in contribution of α- F e phase and also revealed the presence of various iron oxides (maghemite, magnetite, hematite and wűstite).

  12. 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.

  13. Syntheses, characterization and antioxidant activity studies of mixed-ligand copper(II) complexes of 2,2‧-bipyridine and glycine: The X-ray crystal structure of [Cu(BPy)(Gly)]ClO4

    NASA Astrophysics Data System (ADS)

    Ibrahim, Mohamed M.; Ramadan, Abd El-Motaleb M.; Shaban, Shaban Y.; Mersal, Gaber A. M.; El-Shazly, Samir A.; Al-Juaid, Salih

    2017-04-01

    A series of mixed-ligand complexes, viz., [CuLL'X]Y {L = bipyridine; L' = glycine; X = 0, Y = ClO4- (1); X = Cl, Y = 2H2O (2); X = H2O, Y = NO3- (3); X = CH3COO-, Y = H2O (4)} and {[Cu(Gly)(BPy)]2-μ-(SO4)}(5)} have been synthesized and characterized by means of elemental analysis, spectroscopic (FT-IR, UV-Vis and ESR), and thermal analysis, as well as magnetic moment measurements. Spectral and X-ray structural features led to the conclusion that complexes 2-5 have square-pyramidal environments around copper(II) center with coordination chromophores CuN3OCl and CuN3O2, respectively. Whereas complex 1 displays square planar geometry. The quasi-reversible CuII/CuI redox couple slightly improves its reversibility with considerable decrease in current intensity. Additionally, the antioxidant (superoxide dismutase and catalase) biomimetic catalytic activities of the obtained complexes have been tested and found to be promising candidates as dual functional mimic enzyme to serve for complete reactive oxygen species (ROS) detoxification, both with respect to the superoxide radicals and the related peroxides.

  14. 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.

  15. A Study on the Electrodeposited Cu-Zn Alloy Thin Films

    NASA Astrophysics Data System (ADS)

    Özdemir, Rasim; Karahan, İsmail Hakkı; Karabulut, Orhan

    2016-11-01

    In this article, electrochemical deposition of the nanocrystalline Cu1- x Zn x alloys on to aluminum substrates from a non-cyanide citrate electrolyte at 52.5, 105, 157.5, and 210 A m-2 current densities were described. The bath solution of the Cu1- x Zn x alloys consisted of 0.08 mol L-1 CuSO4·5H2O, 0.2 mol L-1 ZnSO4·7H2O, and 0.5 mol L-1 Na3C6H5O7. The effect of the current density on the microstrain, grainsize, phase structure, and DC electrical resistivity behavior was investigated. The electrolyte was investigated electrochemically by cyclic voltammetry (CV) studies. A scanning electron microscope (SEM) was used to study the morphologies of the deposits. Deposited alloys were investigated by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and four-point probe electrical resistivity techniques. With an increase in applied current density values from 52.5 to 210 A m-2, the amount of deposited copper in the alloy was decreased significantly from 65.5 to 16.6 pct and zinc increased from 34.4 to 83.4 pct. An increase in the current density was accompanied by an increase in grain size values from 65 to 95 nm. SEM observations indicated that the morphology of the film surface was modified to bigger grained nanostructures by increasing the current density. The XRD analysis showed alloys have a body-centered cubic (bcc) crystal structure with preferential planes of (110) and (211). Furthermore, four-point measurements of the films revealed that the resistivity of the deposited films was tailored by varying current densities in the electrolyte.

  16. 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.

  17. ESR Steels for Defence - State of the Art. MRL Seminar, held December 14, 1982,

    DTIC Science & Technology

    1983-05-01

    specially shaped moulds. PROPERTIES OF ESR STEELS Consideration is given to the high-strength, quenched and tempered steels of the En 25/AISI 4340 type...furnace and ESR samples of AISI 4340 and En25 steers with sulphur contents ranging from 0.002-0.025 wt.%. Corrosion of rotating discs of all steels in...AD-A132 993 ESR STEELS FOR DEFENCE -STATE OF THE ART URL SEMINAR 1/1 HELD DECEMBER 14 19821U) MATERIALS RESEARCH LAOS ASCOT YALE (AUSTRALIA) R .J 0

  18. 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.

  19. 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.

  20. Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

    NASA Astrophysics Data System (ADS)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2012-02-01

    The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. 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. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

  1. Optical and structural studies of CuI clusters in zeolites LTA and FAU

    NASA Astrophysics Data System (ADS)

    Kodaira, Tetsuya; Ikeda, Takuji

    2006-05-01

    CuI clusters were incorporated into α-cages and supercages of zeolites LTA and FAU, respectively, with various loading densities. From the powder XRD measurement of CuI clusters in FAU, it can be concluded that CuI clusters with homogeneous size were distributed in the cages. In case of using FAU as a host, when the loading density became close to the maximum, photo absorption intensity gradually decreased. A polariton effect, i.e. photo excited energy transfers among the clusters, may play an important role on this phenomenon. Cu and I atoms of bulk CuI crystal have tetrahedral chemical bondings. Supercages of FAU have an arrangement of a diamond structure. Coincidence on the symmetry of the chemical bondings in the CuI clusters and the arrangement of the clusters in the supercages may be the origin of a highly ordered state of CuI clusters and will enhance the polariton effect.

  2. Composition- and temperature-dependent liquid structures in Al-Cu alloys: an ab initio molecular dynamics and x-ray diffraction study

    NASA Astrophysics Data System (ADS)

    Xiong, L. H.; Wang, X. D.; Cao, Q. P.; Zhang, D. X.; Xie, H. L.; Xiao, T. Q.; Jiang, J. Z.

    2017-01-01

    The composition- and temperature-dependent liquid structures in eight Alrich-Cu binary alloys (from hypoeutectic Al93Cu7 to hypereutectic Al70Cu30) have been experimentally and computationally studied by x-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. The remarkable agreements of structure factors for all liquid Alrich-Cu alloys obtained from high-temperature high-energy XRD measurements and AIMD simulations have been achieved, which consolidates the analyses of structural evolutions in Alrich-Cu liquids during the cooling processing by AIMD simulations. The heat capacity of liquid Alrich-Cu alloys continuously increases and presents no abnormal peak when reducing the temperature, which differs from the reported prediction for 55-atom Alrich-Cu nanoliquids. The diffusivities of Al and Cu undergo an increasing deviation from Arrhenius behavior by tuning Cu concentration from 7 to 30 atomic percentages, correlated to the local ordering in these liquids by means of coordination number, bond-angle distribution, Honeycutt-Andersen index, bond-orientational order and Voronoi tessellation analyses. Upon cooling, the microstructure of the liquid Alrich-Cu alloys inclines to form Al2Cu crystal-like local atomic ordering, especially in the hypereutectic liquids. The favorable short-range ordering between Cu and Al atoms could cause the non-Arrhenius diffusion behavior.

  3. Model-based analysis for kinetic complexation study of Pizda and Cu(II)

    NASA Astrophysics Data System (ADS)

    Vosough, M.; Maeder, M.; Jalali-Heravi, M.; Norman, S. E.

    2008-08-01

    In the present work, the multivariate kinetic complexation of a new synthesized ligand, 1-(2″-hydroxyl cyclohexyl)-3'-[aminopropyl]-4-[3'-aminopropyl]piperazine (Pizda) and Cu 2+ in 50% ethanol-water solution is investigated using the UV-vis stopped-flow technique and state-of-the-art multi-wavelength numerical analysis. Model-based least squares fitting analysis or hard modeling is a specific part of chemometrics which is based on mathematical relationships for describing the measurements. Some recent developments include the incorporation of the effects of non-ideal experimental conditions into the fitting algorithm so it can substantially simplify experimental procedures. In this study no buffers are required because pH changes are taken into computations. Some 21 multi-wavelength kinetic measurements, taken at various initial concentrations of [H +] were analyzed globally, i.e. simultaneously applying an all inclusive reaction mechanism and a common set of species spectra. Using numerical analysis, the pH of the experimental solutions was allowed to vary as a consequence of the proceeding reactions. This enabled the complete kinetic analysis of the formation and dissociation of Cu(Pizda) n+ . Here protonation equilibria have been directly incorporated into the rate law, so thus variable pH values have been allowed during each measurement. Using the independently estimated stability constants (from spectrophotometric and potentiometric measurements) for the Cu(Pizda) n+ complexes, a total of six rate constants and one protonation constant could be elucidated. The results of the analysis include the concentration distribution and spectra of all chemical species involved in the reaction. A low standard deviation and residual profiles obtained validate the results.

  4. Model-based analysis for kinetic complexation study of Pizda and Cu(II).

    PubMed

    Vosough, M; Maeder, M; Jalali-Heravi, M; Norman, S E

    2008-08-01

    In the present work, the multivariate kinetic complexation of a new synthesized ligand, 1-(2''-hydroxyl cyclohexyl)-3'-[aminopropyl]-4-[3'-aminopropyl]piperazine (Pizda) and Cu(2+) in 50% ethanol-water solution is investigated using the UV-vis stopped-flow technique and state-of-the-art multi-wavelength numerical analysis. Model-based least squares fitting analysis or hard modeling is a specific part of chemometrics which is based on mathematical relationships for describing the measurements. Some recent developments include the incorporation of the effects of non-ideal experimental conditions into the fitting algorithm so it can substantially simplify experimental procedures. In this study no buffers are required because pH changes are taken into computations. Some 21 multi-wavelength kinetic measurements, taken at various initial concentrations of [H(+)] were analyzed globally, i.e. simultaneously applying an all inclusive reaction mechanism and a common set of species spectra. Using numerical analysis, the pH of the experimental solutions was allowed to vary as a consequence of the proceeding reactions. This enabled the complete kinetic analysis of the formation and dissociation of Cu(Pizda)(n+). Here protonation equilibria have been directly incorporated into the rate law, so thus variable pH values have been allowed during each measurement. Using the independently estimated stability constants (from spectrophotometric and potentiometric measurements) for the Cu(Pizda)(n+) complexes, a total of six rate constants and one protonation constant could be elucidated. The results of the analysis include the concentration distribution and spectra of all chemical species involved in the reaction. A low standard deviation and residual profiles obtained validate the results.

  5. Approach to study of Cu, Ni and Zn content in soil for ecotoxicological risk assessment

    NASA Astrophysics Data System (ADS)

    Boluda, R.; Marimon, L.; Gil, C.; Roca-Pérez, L.

    2009-04-01

    Current Spanish legislation on contaminated soils defines contaminated soil as "that whose characteristics have been negatively altered by the presence of dangerous human-derived chemical components whose concentration is such that it is an unacceptable risk for human health or the environment and has been expressly declared as such by legal ruling". Regarding heavy metals, the Spanish Autonomous Communities will promote measures to obtain generic reference values to declare a soil to be contaminated. In the Valencian Community, these reference values still do not exist. So if the protection of ecosystems is considered a priority to declare a soil to be contaminated and to assess the level of risk, emergency toxicity tests and seed growth in land plants are resorted to, or tests with aquatic organisms or other experiments with leached soils obtained by standard procedures are carried out. We studied the toxic effects of calcareous contaminated soils by Cu, Ni and Zn on marine bacterium Vibrio fisheri (MicrotoxR test assay) (1) and on barley (Hordeum vulgare L.) in plate (germination index) (2) and pot (UNE 77301) (3) experiments for the purpose of establishing the Cu, Ni and Zn concentrations in soil which may lead to toxicity in order to observe, therefore, whether there is any likelihood of these pollutants coming into contact with any receptor and if adverse effects exist for living beings and the environment. The results showed significant differences among the three types of tests done but, in all cases, the concentrations needed to reflect toxicity effect on organisms were around 20 -70 (Cu and Ni) to 1000 (Zn) times higher than the levels of the control soils. The sensitivity order of the bio-assay was: (1) < (3) < (2). We would like to thank Spanish government-MICINN for partial funding and support (MICINN, project CGL2006-09776).

  6. First-principles study of defect formation in the photovoltaic semiconductors Cu2GeS3 and Cu2ZnGeS4 for comparison with Cu2SnS3, Cu2ZnSnS4, and CuInSe2

    NASA Astrophysics Data System (ADS)

    Nishihara, Hironori; Maeda, Tsuyoshi; Shigemi, Akio; Wada, Takahiro

    2017-04-01

    The formation energies of neutral Cu, Ge, and S vacancies in monoclinic Cu2GeS3 and those of neutral Cu, Zn, Ge, and S vacancies in kesterite-type Cu2ZnGeS4 were evaluated by first-principles pseudopotential calculations using plane-wave basis functions. The calculations were performed at typical points in a schematic ternary phase diagram of a Cu–Ge–S system for Cu2GeS3 and in Cu–(Zn1/2Ge1/2)–S and Cu29S16–ZnS–GeS2 pseudoternary phase diagrams for Cu2ZnGeS4. The results have been compared with those for Cu2SnS3, Cu2ZnSnS4, and CuInSe2 calculated with the same version of the CASTEP program code. The results indicate that Cu vacancies are easily formed in Cu2GeS3 and Cu2ZnGeS4 under the Cu-poor condition as in the cases of Cu2SnS3, Cu2ZnSnS4, and CuInSe2, suggesting that Cu2GeS3 and Cu2ZnGeS4 are also preferable p-type absorber materials for thin-film solar cells. Desirable preparation conditions of these thin films for photovoltaic application are discussed using the calculated formation energies of antisite defects.

  7. Structural and dc electrical resistivity study of Gd 3+-substituted Cu-Cd mixed ferrites

    NASA Astrophysics Data System (ADS)

    Kolekar, C. B.; Kamble, P. N.; Vaingankar, A. S.

    1994-11-01

    Polycrystalline ferrite compositions of Cd xCu 1- xFe 2- yGd yO 4 ( x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0; y = 0.0 and 0.1) were prepared by the standard ceramic technique. The X-ray crystallographic study was done using filtered Cu K α radiation. From the diffractograms it is observed that for x ⩾ 0.2 compounds are cubic spinels, while for x = 0 they are tetragonal, and the dependence of the lattice constant on cadmium concentration obeys Vegard's law. The infrared absorption of the powder samples shows two strong absorption bands in the frequency range 400-600 cm -1, and the analysis shows that Gd occupies 'B' sites. The chemical analysis was done by atomic absorption spectroscopy. The dc resistivity study shows an increase in Δ E values and thus in the resistivity after Gd 3+ substitution, suggesting that even though Gd 3+ occupies 'B' sites it does not take part in the conduction mechanism, but impedes it.

  8. Passive optical limiting studies of nanostructured Cu doped ZnO-PVA composite thin films

    NASA Astrophysics Data System (ADS)

    Tamgadge, Y. S.; Sunatkari, A. L.; Talwatkar, S. S.; Pahurkar, V. G.; Muley, G. G.

    2016-01-01

    We prepared undoped and Cu doped ZnO semiconducting nanoparticles (NPs) by chemical co-precipitation method and obtained Cu doped ZnO-polyvinyl alcohol (PVA) nanocomposite thin films by spin coating to investigate third order nonlinear optical and optical limiting properties under cw laser excitation. Powder samples of NPs were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy, transmission electron microscopy, ultraviolet-visible (UV-vis) and Fourier transform infrared spectroscopy. XRD pattern and FE-SEM micrograph revealed the presence of hexagonal wurtzite phase ZnO NPs having uniform morphology with average particle size of 20 nm. The presence of excitons and absorption peaks in the range 343-360 nm, revealed by UV-vis study, were attributed to excitons in n = 1 quantum state. Third order NLO properties of all composite thin films were investigated by He-Ne continuous wave (cw) laser of wavelength 632.8 nm using Z-scan technique. Thermally stimulated enhanced values of nonlinear refraction and absorption coefficients were obtained which may be attributed to self-defocusing effect, reverse saturable absorption, weak free carrier absorption and surface states properties originated from thermo optic effect. Optical limiting properties have been studied using cw diode laser of wavelength 808 nm and results are presented.

  9. Synthesis and characterization of novel Cu (II) complexes with 3-substituted-4-amino-5-mercapto-1,2,4-triazole Schiff bases: A new route to CuO nanoparticles

    NASA Astrophysics Data System (ADS)

    Aly, Hisham M.; Moustafa, Moustafa E.; Nassar, Moustafa Y.; Abdelrahman, Ehab A.

    2015-04-01

    Cu (II) complexes, were synthesized with newly derived biologically active 1,2,4-triazole Schiff bases. The Schiff bases were synthesized by condensation of 3-substituted-4-amino-5-mercapto-1,2,4-triazole with dibenzoylmethane. The synthesized compounds were characterized using elemental analysis, magnetic moment, thermal analysis and spectral tools (FT-IR, 1HNMR, ESR, and UV-Vis spectroscopy). All the synthesized complexes are nonelectrolytes in N,N-dimethylformamide. The synthesized Schiff bases and their Cu (II) complexes have been screened for antibacterial (Escherichia coli &Staphylococcus aureus) and antifungal (Aspergillus flavus &Candida albicans) activity using a modified Bauer-Kirby method. Interestingly, the synthesized Cu (II) complexes were used as precursors for CuO nanoparticles which were characterized using XRD, HR-TEM, FT-IR and UV-Vis spectroscopy. The photocatalytic activity of the prepared CuO nanoparticles was studied by performing the degradation of methylene blue dye under UV illumination in the presence of H2O2 and the results showed that the maximum percent of the degradation of methylene blue dye (MB) was found 96.18% after 360 min.

  10. Fabrication, characterization, and kinetic study of vertical single-crystalline CuO nanowires on Si substrates

    PubMed Central

    2012-01-01

    We report here on the first study of the growth kinetics of high-yield, vertical CuO nanowires on silicon substrates produced by the process of thermal oxidation. The length of the CuO nanowires could be tuned from several to tens of micrometers by adjusting the oxidation temperature and time. The grown CuO nanowires were determined to be single-crystalline with different axial crystallographic orientations. After a series of scanning electron microscopy examinations, the average length of CuO nanowires produced at each temperature was found to follow a parabolic relationship with the oxidation time. The parabolic growth rate at different oxidation temperatures was measured. The activation energy for the growth of CuO nanowires calculated from an Arrhenius plot was found to be about 174.2 kJ/mole. In addition, the current-voltage characterization indicated that the sample with high-density CuO nanowires exhibited ohmic behavior, and its resistance was found to significantly decrease with increasing environmental temperature. The result can be attributed to an increase in the number of carriers at higher temperatures. PMID:22330902

  11. Interaction of NH3 with Cu-SSZ-13 Catalyst: A Complementary FTIR, XANES, and XES Study.

    PubMed

    Giordanino, Filippo; Borfecchia, Elisa; Lomachenko, Kirill A; Lazzarini, Andrea; Agostini, Giovanni; Gallo, Erik; Soldatov, Alexander V; Beato, Pablo; Bordiga, Silvia; Lamberti, Carlo

    2014-05-01

    In the typical NH3-SCR temperature range (100-500 °C), ammonia is one of the main adsorbed species on acidic sites of Cu-SSZ-13 catalyst. Therefore, the study of adsorbed ammonia at high temperature is a key step for the understanding of its role in the NH3-SCR catalytic cycle. We employed different spectroscopic techniques to investigate the nature of the different complexes occurring upon NH3 interaction. In particular, FTIR spectroscopy revealed the formation of different NH3 species, that is, (i) NH3 bonded to copper centers, (ii) NH3 bonded to Brønsted sites, and (iii) NH4(+)·nNH3 associations. XANES and XES spectroscopy allowed us to get an insight into the geometry and electronic structure of Cu centers upon NH3 adsorption, revealing for the first time in Cu-SSZ-13 the presence of linear Cu(+) species in Ofw-Cu-NH3 or H3N-Cu-NH3 configuration.

  12. Adsorption kinetic and equilibrium study for removal of mercuric chloride by CuCl2-impregnated activated carbon sorbent.

    PubMed

    Li, Xin; Liu, Zhouyang; Lee, Joo-Youp

    2013-05-15

    The intrinsic adsorption kinetics of mercuric chloride (HgCl2) was studied for raw, 4% and 10% CuCl2-impregnated activated carbon (CuCl2-AC) sorbents in a fixed-bed system. An HgCl2 adsorption kinetic model was developed for the AC sorbents by taking into account the adsorption kinetics, equilibrium, and internal and external mass transfer. The adsorption kinetic constants determined from the comparisons between the simulation and experimental results were 0.2, 0.3, and 0.5m(3)/(gs) for DARCO-HG, 4%(wt), and 10%(wt) CuCl2-AC sorbents, respectively, at 140 °C. CuCl2 loading was found to slightly increase the adsorption kinetic constant or at least not to decrease it. The HgCl2 equilibrium adsorption data based on the Langmuir isotherm show that high CuCl2 loading can result in high binding energy of the HgCl2 adsorption onto the carbon surface. The adsorption equilibrium constant was found to increase by ~10 times when CuCl2 loading varied from 0 to 10%(wt), which led to a decrease in the desorption kinetic constant (k2) by ~10 times and subsequently the desorption rate by ~50 times. Intraparticle pore diffusion considered in the model showed good accuracy, allowing for the determination of intrinsic HgCl2 adsorption kinetics.

  13. Two-dimensional Fourier transform ESR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Gorcester, Jeff; Freed, Jack H.

    1988-04-01

    We describe our pulsed two-dimensional Fourier transform ESR experiment and demonstrate its applicabilty for the double resonance of motionally narrowed nitroxides. Multiple pulse irradiation of the entire nitroxide spectrum enables the correlation of two precessional periods, allowing observation of cross correlations between hyperfine lines introduced by magnetization transfer in the case of a three-pulse experiment (2D ELDOR), or coherence transfer in the case of a two-pulse experiment (COSY). Cross correlations are revealed by the presence of cross peaks which connect the autocorrelation lines appearing along the diagonal ω1=ω2. The amplitudes of these cross peaks are determined by the rates of magnetization transfer in the 2D ELDOR experiment. The density operator theory for the experiment is outlined and applied to the determination of Heisenberg exchange (HE) rates in 2,2,6,6-tetramethyl-4-piperidone-N-oxyl-d15 (PD-tempone) dissolved in toluene-d8. The quantitative accuracy of this experiment is established by comparison with the HE rate measured from the dependence of the spin echo T2 on nitroxide concentration.

  14. Anisotropic embrittlement in high-hardness ESR 4340 steel forgings

    SciTech Connect

    Olson, G.B.; Anctil, A.A.; DeSisto, T.S.; Kula, E.B.

    1983-08-01

    ESR 4340 steel forgings tempered to a hardness of HRC 55 exhibit a severe loss of tensile ductility in the short transverse direction which is strain-rate and humidity dependent. The anisotropy is also reflected in blunt-notch Charpy impact energy, but is absent in the sharp-crack fracture toughness. Brittle behavior is associated with regions of smooth intergranular fracture aligned with microstructural banding Scanning Auger microprobe analysis indicates intergranular segregation of phosphorus and sulfur. The anisotropic embrittlement is attributed to an interaction of nonequilibrium segregation on solidification with local equilibrium segregation at grain boundaries during austenitizing. The regions are prone to brittle fracture under impact conditions and abnormal sensitivity to environmental attack during low strain-rate deformation. A relatively sparse distribution of these defects accounts for the discrepancy between smooth bar and blunt-notch tests vs sharp-crack tests. Isotropic properties are restored by homogenization treatment. For application of these steels at extreme hardness levels, homogenization treatment is essential.

  15. Anisotropie embrittlement in high-hardness ESR 4340 steel forgings

    NASA Astrophysics Data System (ADS)

    Olson, G. B.; Anctil, A. A.; Desisto, T. S.; Kula, E. B.

    1983-08-01

    ESR 4340 steel forgings tempered to a hardness of HRC 55 exhibit a severe loss of tensile ductility in the short transverse direction which is strain-rate and humidity dependent. The anisotropy is also reflected in blunt-notch Charpy impact energy, but is absent in the sharp-crack fracture toughness. Brittle behavior is associated with regions of smooth intergranular fracture which are aligned with microstructural banding. Scanning Auger microprobe analysis indicates some intergranular segregation of phosphorus and sulfur in these regions. The anisotropic embrittlement is attributed to an interaction of nonequilibrium segregation on solidification with local equilibrium segregation at grain boundaries during austenitizing. This produces defective regions of enhanced intergranular impurity segregation which are oriented during forging. The regions are prone to brittle fracture under impact conditions and abnormal sensitivity to environmental attack during low strain-rate deformation. A relatively sparse distribution of these defects (˜10cm-3) accounts for the discrepancy between smooth bar and blunt-notch tests vs sharp-crack tests. Isotropie properties are restored by homogenization treatment. For application of these steels at extreme hardness levels, homogenization treatment is essential.

  16. Chlorophyll a triplet-state ESR in frozen phosphatidylcholine vesicles

    SciTech Connect

    Hiromitsu, I.; Kevan, L.

    1988-05-19

    Photoexcited chlorophyll a (Chla) triplet state in rapidly frozen egg phosphatidylcholine (EPC) vesicles is investigated at 77 K by electron spin resonance (ESR) spectroscopy using light intensity modulation. The electron spin polarization (ESP) intensity is stronger for 0.2 mM Chla than for 1.0 mM Chla. The absolute values of the zero field splitting parameter, D, are 283 (+/-1) x 10/sup -4/ and 276 (+/-2) x 10/sup -4/ cm/sup -1/, and the average depopulation rates of the triplet state are 0.671 +/- 0.052 and 1.054 +/- 0.036 ms/sup -1/ for 0.2 mM Chla and 1.0 mM Chla, respectively. This difference can be consistently attributed to faster triplet-state migration between adjacent Chla's at the higher 1.0 mM Chla concentration. A characteristic migration time of 2.6 ms is obtained. The ESP pattern of the Chla triplet state in the frozen EPC vesicles resembles that in polycrystals more than that in glasses. This suggests that the local environment around Chla in the vesicles is more structured than in glasses.

  17. Magnetism of coherent Co and Ni thin films on Cu(111) and Au(111) substrates: An ab initio study

    NASA Astrophysics Data System (ADS)

    Zelený, Martin; Dlouhý, Ivo

    2017-02-01

    We present an ab initio study of structural and magnetic properties of coherent Co and Ni thin films on Cu(111) and Au(111) substrates with thicknesses of up to 6 monolayers. All studied films on Cu(111) substrates prefer structures close their ground state (hcp for Co and fcc for Ni), whereas only the hcp stacking sequence has been found for both films on Au(111) substrates. All studied films exhibit instability of the first monolayer with respect to decomposition into 2-monolayer- or 3-monolayer-high islands, which is in agreement with experimental findings. All studied films are also ferromagnetic, nevertheless the Ni/Cu(111) films reduce their magnetic moments in the layer adjacent to the substrate due to a stronger Cu-Ni interaction at the interface. The magnetic anisotropy of a Co film does not depend on the film thickness: all the studied Co/Au(111) films exhibit a perpendicular magnetic anisotropy, whereas all the Co/Cu(111) films prefer in-plane magnetization. On the other hand, both Ni films change their preference for in-plane orientation of their easy axis to out-of-plane orientation at a critical thickness of 2 monolayers, however, the magnetic anisotropy energies for films thicker than 1 monolayer are smaller than 1 meV/Ni atom. These behaviors of magnetic anisotropy do not depend on the structure of the studied films.

  18. The rotational spectrum of CuCCH(X̃  1Σ+): a Fourier transform microwave discharge assisted laser ablation spectroscopy and millimeter/submillimeter study.

    PubMed

    Sun, M; Halfen, D T; Min, J; Harris, B; Clouthier, D J; Ziurys, L M

    2010-11-07

    The pure rotational spectrum of CuCCH in its ground electronic state (X̃  (1)Σ(+)) has been measured in the frequency range of 7-305 GHz using Fourier transform microwave (FTMW) and direct absorption millimeter/submillimeter methods. This work is the first spectroscopic study of CuCCH, a model system for copper acetylides. The molecule was synthesized using a new technique, discharge assisted laser ablation spectroscopy (DALAS). Four to five rotational transitions were measured for this species in six isotopologues ((63)CuCCH, (65)CuCCH, (63)Cu(13)CCH, (63)CuC(13)CH, (63)Cu(13)C(13)CH, and (63)CuCCD); hyperfine interactions arising from the copper nucleus were resolved, as well as smaller splittings in CuCCD due to deuterium quadrupole coupling. Five rotational transitions were also recorded in the millimeter region for (63)CuCCH and (65)CuCCH, using a Broida oven source. The combined FTMW and millimeter spectra were analyzed with an effective Hamiltonian, and rotational, electric quadrupole (Cu and D) and copper nuclear spin-rotation constants were determined. From the rotational constants, an r(m)(2) structure for CuCCH was established, with r(Cu-C) = 1.8177(6) Å, r(C-C) = 1.2174(6) Å, and r(C-H) = 1.046(2) Å. The geometry suggests that CuCCH is primarily a covalent species with the copper atom singly bonded to the C≡C-H moiety. The copper quadrupole constant indicates that the bonding orbital of this atom may be sp hybridized. The DALAS technique promises to be fruitful in the study of other small, metal-containing molecules of chemical interest.

  19. Magnetic properties of the Ni-Cu-Zn system doped with magnesium oxide

    NASA Astrophysics Data System (ADS)

    Hemeda, O. M.; Tawfik, A.; Hemeda, D. M.; Elsheekh, A. M.

    2015-09-01

    A series of ferrite samples, Ni0.1Cu0.2MgxZn0.7-x Fe2O4, (x=0.00, 0.15, 0.25, 0.35, 0.45, 0.55 and 0.70) has been prepared by the standard ceramic technique, sintered at 1200 °C for 2 h, and their crystalline structures were investigated by using X-ray diffraction. The IR spectra and the ESR spectra analysis have been studied. DC electrical resistivity, thermoelectric power, charge carriers concentration and charge carrier mobility have been calculated at different temperatures. The value of dc electrical resistivity reach minimum at x=0.35 and above this value the electrical resistivity start to increase. It is noticed that thermoelectric power α for the "Ni-Cu-Zn" system exhibits a positive sign indicating the majority carriers are holes without excluding the presence of electrons. Saturation magnetization Ms for the "Ni-Cu-Zn" system was calculated from M-H loop. It is noted that Ms decreases with Mg content up to x=0.55 and rapidly decrease above x>0.55 for the "Ni-Cu-Zn" system.

  20. "Labrador-Dose" dosimetry system based on a coherent superheterodyne ESR spectrometer

    NASA Astrophysics Data System (ADS)

    Cherepanov, A.; Popova, M.; Tyshchenko, I.; Vakhnin, D.

    2016-09-01

    A new (coherent heterodin) type ESR-spectrometer recently invented in Ural Federal University is described. Application of the spectrometer for measuring high dose ionizing radiation by means of alpha-alanin storage detectors is considered.

  1. Field-dependent Collective ESR Mode in YbRh2Si2

    SciTech Connect

    Petrovic, C.; Holanda, L.M.; Duque, J.G.S.; Bittar, E.M.; Adriano, C.; Pagliuso, P.G.; Rettori, C.; Hub, R.W.; Maquilon, S.; Fisk, Z.; Huber, D.L.; Oseroff, S.B.

    2009-10-15

    Electron spin resonance (ESR) experiments in YbRh{sub 2}Si{sub 2} Kondo lattice (T{sub K} {approx_equal} 25 K) at different field/frequencies (4.1 {le} v {le} 34.4 GHz) and H{sub {perpendicular}c} revealed: (i) a strong field dependent Yb{sup 3+} spin-lattice relaxation, (ii) a weak field and T-dependent effectiveg-value, (iii) a suppression of the ESR intensity beyond 15% of Lu-doping, and (iv) a strong sample and Lu-doping ({le}15%) dependence of the ESR data. These results suggest that the ESR signal in YbRh{sub 2}Si{sub 2} may be due to a coupled Yb{sup 3+}-conduction electron resonant collective mode with a subtle field-dependent spins dynamic.

  2. Selective photo-deposition of Cu onto the surface of monodisperse oleic acid capped TiO2 nanorods probed by FT-IR CO-adsorption studies.

    PubMed

    Hikov, Todor; Schroeter, Marie-Katrin; Khodeir, Lamma; Chemseddine, Abdelkrim; Muhler, Martin; Fischer, Roland A

    2006-04-07

    A novel, non-aqueous, organometallic route to nanocomposite Cu@TiO2 materials is presented. TiO2 nanorods stabilized with oleic acid (OLA) were used as support for the photo-assisted deposition of Cu using the organometallic Cu(II) precursor [Cu(OCH(CH3)CH2N(CH3)2)2] (1). The copper precursor penetrates through the shell of OLA and is photo reduced to deposit Cu0 directly at the surface of the TiO2 rods. The obtained Cu decorated nanorods were still soluble in nonpolar organic solvents without change of the morphology of nanorods. The Cu@TiO2 colloid was characterized by means of UV-VIS, XRD, AAS, and HRTEM. FTIR CO adsorption studies provide evidence for Cu0 anchored at the titania surface by a characteristic absorption at 2084 cm-1. Comparative studies of Cu-deposition were performed using CuCl2 as simple Cu source which proved that the concept of organometallic disguise of the metal centre results in a higher reaction rate and the circumvention of non-selective reduction, parasitic side reactions and undesired agglomeration of the OLA stabilized titania nanorods.

  3. [Results of a longitudinal study on the psychological acceptance of contraception with Multiload Cu 250].

    PubMed

    Rauchfleisch, U

    1982-01-01

    This article assesses the psychological aspects of 6 months' use of Multiload Cu 250 IUDs inserted in 51 patients aged 19-46 years at the sociomedical service of the university women's clinic at Basel. At the time of insertion the gynecologist completed a questionnaire designed by the author and the patients completed the Fribourg Personality Inventory and the Rosenzweig Picture-Frustration Test. At follow-up visits 6-8 weeks and 6 months later, patients were questioned on their complications, perceived changes in fear of becoming pregnant, sexual satisfaction, and their general impression of the IUD. The rate of complications at 6 months was 37%, primarily prolonged bleeding, breakthrough bleeding, and cramps. The statistical correlation between complications and different socioeconomic parameters was not established, but the highest rate of complications was in women who already had experienced complications with other methods of contraception. After 6 months, the fear of pregnancy had strongly diminished: the proportion fearing pregnancy declined from 35 to 4%. The proportion reporting satisfactory sexual relationships increased from 78% to 94%, and 94% of patients considered contraception with the Multiload Cu 250 to be satisfactory. The patients with the highest rates of complications were those torn between the desire for a pregnancy and the absolute desire not to conceive during the time of the study. The author proposes the hypothesis that complications are the somatic manifestation of repressed conflict.

  4. Study of polyaniline coated CuFe2O4 nanoparticles and their application in biosensor

    NASA Astrophysics Data System (ADS)

    Sharma, Uma Shankar; Shah, Rashmi

    2016-05-01

    Polyaniline coated with nanoferrite particles has attractive application in enzyme less biosensor. In this paper, we have reported the synthesis of copper ferrite by Chemical Coprecipitation method and polymerization of polyaniline by oxidation method. The polyaniline-ferrite composite was characterized by different techniques such as XRD and VSM. The XRD pattern confirmed the presence of cubic phase and particles size in nano scale. The magnetic properties were studied by vibrating sample magnetometer (VSM) technique at room temperature. The higher values of saturation magnetization attributed to the cation distribution change from normal to spinel structure. Some Fe3+ ions drifted from octahedral site to tetrahedral site through the conversion of some Fe2+ ions to Fe3+ ions with super-exchange interactions and gives rise to saturation magnetization. The saturation magnetization of polyaniline coated CuFe2O4 using ammonium nitrate is much less than by polyaniline coated CuFe2O4 using ammonium peroxidisulphate. The saturation magnetization Ms of the nanocomposite is dependent on the volume fraction of the magnetic ferrite particles and on the contribution of the non-magnetic polyaniline coated layer. Polyaniline worked as an immobilization layer in the enzyme less biosensor because enzyme less biosensor is not affected by environmental factor.

  5. Has NHS reorganisation saved lives? A CuSum study using 65 years of data

    PubMed Central

    Lale, Alice S

    2016-01-01

    Objectives To determine if NHS reforms affect population mortality. Design Retrospective study using routinely published data. Setting & participants Resident population of England and Wales 1948 to 2012 Main outcome measure All cause age sex directly standardised mortality England and Wales 1948 to 2012. Methods Using the CuSum technique and Change-Point Analysis to identify sustained changes in the improving age-standardised mortality rates for the period 1948-2012, and comparing the time of these changes with periods of NHS reform. Where observed changes did not fit with NHS reform, changes external to the NHS were sought as a possible explanation of changes observed. Results CuSum plotting and CPA showed no significant changes in female mortality trend between 1948 and 2012. However, this analysis identified a sustained improvement in the male mortality trend, occurring in the mid-1970s. A further change in the rate of male mortality decline was found around the Millennium. Conclusion The 1974 NHS reorganisation, changing service arrangements predominantly for women and children, is considered an unlikely explanation of the improved rate of male mortality decline. Thus, centrally led NHS reorganisation has never had any detectable effect on either male or female mortality and must be considered ineffective for this purpose. But some evidence supporting the view that increased funding improves outcomes is found. PMID:26432817

  6. Electronic properties of CuPc and H2Pc: an experimental and theoretical study.

    PubMed

    Nardi, Marco Vittorio; Detto, Francesca; Aversa, Lucrezia; Verucchi, Roberto; Salviati, Giancarlo; Iannotta, Salvatore; Casarin, Maurizio

    2013-08-21

    Phthalocyanine (H2Pc) and its open-shell copper complex (CuPc) deposited on amorphous gold films have been studied by combining the outcomes of several synchrotron based spectroscopic tools (X-ray photoelectron spectroscopy, UV photoelectron spectroscopy and near-edge X-ray absorption fine structure, NEXAFS, spectroscopy) with those of density functional theory (DFT) calculations. The assignment of experimental evidence has been guided by the results of DFT numerical experiments carried out on isolated molecules. With specific reference to CuPc NEXAFS data collected at the N K-edge, they have been assigned by using the open-shell time-dependent DFT (TDDFT) in the framework of the zeroth order regular approximation (ZORA) scalar relativistic approach. The agreement between theory and experiment has been found to be satisfactory, thus indicating that the open-shell TDDFT (F. Wang and T. Ziegler, Mol. Phys., 2004, 102, 2585) may be used with some confidence to look into the X-ray absorption spectroscopy results pertinent to transition metal complexes. As far as the metal-ligand interaction is concerned, the combined use of NEXAFS spectroscopy and DFT outcomes ultimately testified the significant ionic contribution characterizing the bonding between the metal centre and the nitrogen atoms of the phthalocyanine coordinative pocket.

  7. Microstructural and Hardness Studies of Cu-10wt.%Sn Alloy Under Different Aging Conditions

    NASA Astrophysics Data System (ADS)

    Bashir, Farooq; Butt, Muhammad Zakria; Saleemi, Farhat

    2008-02-01

    Microstructure of Cu-10wt.%Sn alloy, prepared by powder metallurgy technique and sintered at 900 °C for 120 min in hydrogen atmosphere, was studied by optical microscopy and XRD technique as a function of aging time. Isothermal aging of the alloy specimens was performed at 250 °C for a period of 30, 60, 120, 300, and 1440 min after solution treatment at 500 °C for 60 min. Rockwell hardness of aged specimens was also measured at room temperature as a function of aging time. It was observed that microstructure of the as-sintered specimens consists of the grains of alpha Cu-Sn solid solution. Moreover, solution treatment of the alloy specimens followed by quenching in water increased the hardness of the as-sintered alloy specimens from 35.5 to 59.8 HRF due to the residual stresses generated by fast cooling. Aging at 250 °C for 30, 60, and 120 min was found to cause a decrease in hardness from 59.8 to 45.1 HRF, whereas the specimens aged for 300 and 1440 min show an increase in hardness from 45.1 to 75.7 HRF. The values of porosity calculated from XRD patterns of the alloy specimens referred to show that porosity varies with aging time in a manner opposite to that of hardness, e.g., porosity is maximum for 120 min aging time where hardness is minimum.

  8. Study of Microstructure and Optical Properties of Pva-Capped ZnS: cu Nanocrystalline Thin Films

    NASA Astrophysics Data System (ADS)

    Thi, Tran Minh; van, Bui Hong; Ben, Pham Van

    A study has been carried out on the Cu doping and PVA capping induced optical property changes in ZnS : Cu nanocrystalline powders and thin film. For this study, ZnS : Cu nanopowders with Cu concentrations of 0.1%, 0.15%, 0.2%, 0.3% and 0.4% are synthesized by the wet chemical method. The polyvinyl alcohol (PVA)-capped ZnS thin film with 0.2% Cu concentration and various PVA concentrations are prepared by the spin-coating method. The microstructures of the samples are investigated by the X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM). The results show that the prepared samples belong to the wurtzite structure with the average particle size of about 3-7 nm. The optical properties of samples are studied by measuring absorption and photoluminescence (PL) spectra in the wavelength range from 300 nm to 900 nm at 300 K. It is shown that the luminescent intensity of ZnS : Cu nanopowders reaches the highest intensity for optimal Cu concentration of 0.2% with the corresponding values of its direct band gap estimated to be about 3.90 eV. While the PVA coating does not affect the microstructure of ZnS nanometerials, the PL spectra of the samples are found to be affected by the PVA concentration as well as the exciting power density. The influence of the polymer coating on the optical properties can be explained by the quantum confinement effect of ZnS nanoparticles in the PVA matrix.

  9. A Meta-Analysis of the Association between ESR1 Genetic Variants and the Risk of Breast Cancer

    PubMed Central

    Yang, Jiaying; Ma, Xu; Dai, Qiaoyun; Huang, Hao; Wang, Lina; Liu, Pei

    2016-01-01

    Background Single nucleotide polymorphisms (SNPs) in the estrogen receptor gene (ESR1) play critical roles in breast cancer (BC) susceptibility. Genome-wide association studies have reported that SNPs in ESR1 are associated with BC susceptibility; however, the results of recent studies have been inconsistent. Therefore, we performed this meta-analysis to obtain more accurate and credible results. Methods We pooled published literature from PubMed, EMBASE, and Web of Science and calculated odds ratios (ORs) with 95% confidence intervals (CIs) to assess the strength of associations using fixed effects models and random effects models. Twenty relevant case-control and cohort studies of the 3 related SNPs were identified. Results Three SNPs of the ESR1 gene, rs2077647:T>C, rs2228480:G>A and rs3798577:T>C, were not associated with increased BC risk in our overall meta-analysis. Stratified analysis by ethnicity showed that in Caucasians, the rs2228480 AA genotype was associated with a 26% decreased risk of BC compared with the GG genotype (OR = 0.740, 95% CI: 0.555–0.987). The C allele of the rs3798577:T>C variant was associated with decreased BC risk in Asians (OR = 0.828, 95% CI: 0.730–0.939), while Caucasians with this allele were found to experience significantly increased BC risk (OR = 1.551, 95% CI: 1.037–2.321). A non-significant association between rs2077647 and BC risk was identified in all of the evaluated ethnic populations. Conclusion Rs3798577 was associated with an increased risk of BC in Caucasian populations but a decreased risk in Asians. Rs2228480 had a large protective effect in Caucasians, while rs2077647 was not associated with BC risk. PMID:27070141

  10. An impedance study of complex Al/Cu-Al2O3 electrode

    NASA Astrophysics Data System (ADS)

    Denisova, J.; Katkevics, J.; Erts, D.; Viksna, A.

    2011-06-01

    Electrochemical impedance spectroscopy (EIS) was used to investigate different Cu deposition regimes on Al surface obtained by internal electrolysis and to characterize properties of fabricated electrodes. EIS experimental data confirmed that Cu deposition by internal electrolysis is realized and the complex electrode system is obtained. The main difficulty in preparation of Al/Cu electrodes is to prevent aluminium oxidation before and during electrochemical deposition of Cu particles. In this work NaCl, CH3COONa, K2SO4, mono- and diammonium citrate electrolytes were examined to determine their suitability for impedance measurements. Al/Cu-Al2O3 electrode composition was approved by equivalent circuit analysis, optical and scanning electron microscope methods. The most optimal Cu deposition mode using internal electrolysis was determined. The obtained results are promising for future electrochemical fabrication of nanostructures directly on Al surfaces by internal electrolysis.

  11. Thermodynamic and kinetic study of solid state reactions in the Cu-Si system

    NASA Astrophysics Data System (ADS)

    Chromik, R. R.; Neils, W. K.; Cotts, E. J.

    1999-10-01

    It has been shown that significant changes in the course of solid state reactions can be realized by decreasing length scale, temperature, or by varying parent microstructures. In the case of the formation of Cu3Si by interdiffusion of Cu and Si, previous research has shown that over a large temperature range reaction rates are determined by the rate of grain boundary diffusion of Cu through the growing Cu3Si phase. We have examined the effect of replacing crystalline Si with amorphous Si (a-Si) on these solid state reactions, as well as the effect of decreasing the temperatures and length scales of the reactions. Multilayered thin film diffusion couples of Cu and a-Si were prepared by sputter deposition, with most average composite stoichiometries close to that of the equilibrium phase Cu3Si. Layer thicknesses of the two materials were changed such that the modulation (sum of the thickness of one layer of Cu and a-Si), λ, varied between 5 and 160 nm. X-ray diffraction analysis and transmission electron microscopy analysis were used to identify phases present in as prepared and reacted diffusion couples. Complete reactions to form a single phase or mixtures of the three low temperature equilibrium silicides (Cu3Si, Cu15Si4, and Cu5Si) were observed. Upon initial heating of samples from room temperature, heat flow signals were observed with differential scanning calorimetry corresponding to the growth of Cu3Si. At higher temperatures (>525 K) and in the presence of excess Cu, the more Cu-rich silicides, Cu15Si, and Cu5Si formed. Based on differential scanning calorimetry results for samples with average stoichiometry of the phases Cu3Si and Cu5Si, enthalpies of formation of these compounds were measured. Considering the reaction of these phases forming from Cu and a-Si, the enthalpies were found to be -13.6±0.3 kJ/mol for Cu3Si and -10.5±0.6 kJ/mol for Cu5Si. The growth of Cu3Si was found to obey a parabolic growth law: x2=k2t, where x is the thickness of the

  12. Microstructure study of pinning sites of highly (0001) textured Sm(Co,Cu){sub 5} thin films grown on Ru underlayer

    SciTech Connect

    Zhao Haibao; Wang Hao; Liu Xiaoqi; Wang Jianping

    2012-04-01

    In this paper, microstructure study of pinning sites of highly (0001) textured Sm(Co,Cu){sub 5} thin films was presented. Various types of pinning sites were identified, such as voids, grain/matrix boundaries (or crystalline/amorphous boundaries), grain boundaries between crystalline grains, and composition inhomogeneity in grains. One key finding of TEM elemental mapping was that Cu atoms were rich in the inner part of Sm(Co,Cu){sub 5} grains (defined by Sm and Co concentrations), instead of the outer part of grains, such as grain boundaries. Cu served as an alloying element in Sm(Co,Cu){sub 5} grains, not as a doping element to form Cu-rich grain boundaries. A model of Sm(Co,Cu){sub 5} films with lateral graded anisotropy due to composition/crystallization variation can explain the huge difference between the H{sub C} and H{sub K}.

  13. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    SciTech Connect

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Si, Rui; Johnston-Peck, Aaron C.; Martinez-Arias, Arturo; Hanson, Jonathan C.; Senanayake, Sanjaya D.

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), such as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).

  14. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    DOE PAGES

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; ...

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), suchmore » as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).« less

  15. Transport and Cu NMR studies of charge and spin dynamics in PrBa{sub 2}Cu{sub 4}O{sub 8}

    SciTech Connect

    Kikuchi, Jun; Terasaki, Ichiro; Machi, Takato; Seiji, Nobuaki

    1996-11-01

    The charge and spin dynamics in PrBa{sub 2}Cu{sub 4}O{sub 8} are investigated by means of transport and Cu NMR measurements. The magnetoresistance was found to be very small at high temperatures and increase rapidly with decreasing temperature below {approximately}100 K, which may be ascribed to the dimensional crossover from one to two dimensions in the charge transport in the CuO double chains. While the NMR signal from the chain Cu sites persists down to 4.2 K without any appreciable line broadening, the signal from the planar Cu sites disappears below {approximately}250 K indicating the long-range antiferromagnetic order of plane Cu moments. This is consistent with the view of metallic conduction along the quasi one-dimensional CuO chains.

  16. A cluster of noncoding RNAs activates the ESR1 locus during breast cancer adaptation.

    PubMed

    Tomita, Saori; Abdalla, Mohamed Osama Ali; Fujiwara, Saori; Matsumori, Haruka; Maehara, Kazumitsu; Ohkawa, Yasuyuki; Iwase, Hirotaka; Saitoh, Noriko; Nakao, Mitsuyoshi

    2015-04-29

    Estrogen receptor-α (ER)-positive breast cancer cells undergo hormone-independent proliferation after deprivation of oestrogen, leading to endocrine therapy resistance. Up-regulation of the ER gene (ESR1) is critical for this process, but the underlying mechanisms remain unclear. Here we show that the combination of transcriptome and fluorescence in situ hybridization analyses revealed that oestrogen deprivation induced a cluster of noncoding RNAs that defined a large chromatin domain containing the ESR1 locus. We termed these RNAs as Eleanors (ESR1 locus enhancing and activating noncoding RNAs). Eleanors were present in ER-positive breast cancer tissues and localized at the transcriptionally active ESR1 locus to form RNA foci. Depletion of one Eleanor, upstream (u)-Eleanor, impaired cell growth and transcription of intragenic Eleanors and ESR1 mRNA, indicating that Eleanors cis-activate the ESR1 gene. Eleanor-mediated gene activation represents a new type of locus control mechanism and plays an essential role in the adaptation of breast cancer cells.

  17. A cluster of noncoding RNAs activates the ESR1 locus during breast cancer adaptation

    PubMed Central

    Tomita, Saori; Abdalla, Mohamed Osama Ali; Fujiwara, Saori; Matsumori, Haruka; Maehara, Kazumitsu; Ohkawa, Yasuyuki; Iwase, Hirotaka; Saitoh, Noriko; Nakao, Mitsuyoshi

    2015-01-01

    Estrogen receptor-α (ER)-positive breast cancer cells undergo hormone-independent proliferation after deprivation of oestrogen, leading to endocrine therapy resistance. Up-regulation of the ER gene (ESR1) is critical for this process, but the underlying mechanisms remain unclear. Here we show that the combination of transcriptome and fluorescence in situ hybridization analyses revealed that oestrogen deprivation induced a cluster of noncoding RNAs that defined a large chromatin domain containing the ESR1 locus. We termed these RNAs as Eleanors (ESR1 locus enhancing and activating noncoding RNAs). Eleanors were present in ER-positive breast cancer tissues and localized at the transcriptionally active ESR1 locus to form RNA foci. Depletion of one Eleanor, upstream (u)-Eleanor, impaired cell growth and transcription of intragenic Eleanors and ESR1 mRNA, indicating that Eleanors cis-activate the ESR1 gene. Eleanor-mediated gene activation represents a new type of locus control mechanism and plays an essential role in the adaptation of breast cancer cells. PMID:25923108

  18. Spectroscopic studies on the interaction of cysteine capped CuS nanoparticles with tyrosine

    SciTech Connect

    Prasanth, S.; Raj, D. Rithesh; Kumar, T. V. Vineesh; Sudarsanakumar, C.

    2015-06-24

    Biocompatible cysteine coated CuS nanoparticles were synthesized by a simple aqueous solution method. Hexagonal phase of the samples were confirmed from X-ray diffraction and particle size found to be 9 nm. The possible interaction between the bioactive cysteine capped CuS nanoparticles and tyrosine were investigated using spectroscopic techniques such as UV-Visible absorption and fluorescence spectroscopy. It is observed that the luminescence intensity of tyrosine molecule enhanced by the addition CuS nanoparticles.

  19. by Cu Deficiencies

    NASA Astrophysics Data System (ADS)

    Wei, Tian-Ran; Li, Fu; Li, Jing-Feng

    2014-06-01

    This work revealed that the Cu-deficient ternary compounds Cu3- x SbSe4 free of Te and Pb exhibit enhanced thermoelectric performance. Cu3- x SbSe4 ( x = 0, 0.025, 0.050, 0.075) polycrystalline materials with high phase purity were fabricated by a facile method combining mechanical alloying and spark plasma sintering. Effects of Cu deficiencies on crystal structures, microstructures, element chemical states, and thermoelectric properties were systematically studied. High carrier concentration was obtained for the compositions Cu2.95SbSe4 and Cu2.925SbSe4 due to additional Cu vacancies, contributing to a remarkable increase in electrical conductivity. Together with a satisfactorily large Seebeck coefficient above 300 μV/K, a high power factor of about 890 μW/m-K2 at 523 K was achieved for Cu2.95SbSe4 and Cu2.925SbSe4, almost 60% larger than that of the stoichiometric sample with x = 0. The maximum ZT value was increased to 0.50 at 673 K in the Cu2.925SbSe4 sample sintered at a high temperature (703 K); this is the highest value reported so far for the undoped Cu3SbSe4 system.

  20. Photoemission Electron Microscopy Study of Ultrathin FeNi Alloy Films on Cu(111)

    NASA Astrophysics Data System (ADS)

    Sato, Yu; Johnson, Tracey; Giacomo, Jason; Chiang, Shirley; Zhu, Xiangdong; Land, Donald; Nolting, Frithjof; Scholl, Andreas

    2002-03-01

    We are studying the system of FeNi/Cu(111) to understand and control the surface/interface magnetism relevant to the application of the giant magnetoresistive effect to magnetic recording heads. We used the Photoemission Electron Microscope (PEEM2) at the Advanced Light Source to observe the domain structures of the alloy films. PEEM has the unique capability of imaging the film's magnetic structure with high spatial resolution and elemental specificity. At two different thicknesses, we have made sixteen samples and studied the dependence of magnetic structure on varying Fe concentration and substrate quality. Samples with higher Fe content were non-magnetic at room temperature. We speculate this is a structure-driven effect related to the "Invar effect" in the bulk alloy. The PEEM images clearly show that Fe and Ni form a good alloy and have the same domain structures with their magnetization aligned. Further, we find a strong thickness and concentration dependence of the magnetic domain structures.