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Sample records for cu esr studies

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  4. ESR studies of Anatolian gypsum

    NASA Astrophysics Data System (ADS)

    Ulusoy, Ülkü

    2004-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1989-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  7. ESR study of free radicals in mango

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-07-01

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

  9. ESR studies of semicontinuous emulsion polymerization

    SciTech Connect

    Lau, W.; Westmoreland, D.G.

    1993-12-31

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

  10. ESR studies on bleached sedimentary quartz

    NASA Astrophysics Data System (ADS)

    Walther, R.; Zilles, D.

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-08-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1997-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Tuner, H.; Korkmaz, M.

    2007-05-01

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

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

    PubMed

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

    1989-03-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  16. Sonochemical activation of hematoporphyrin: an ESR study.

    PubMed

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

    1994-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    NASA Astrophysics Data System (ADS)

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

    1997-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  20. Metal-containing polyacrylonitriles: ESR studies and conductivity

    SciTech Connect

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

    1995-12-01

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

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

    SciTech Connect

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

    2012-03-15

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

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

    SciTech Connect

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

    2015-06-24

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  4. ESR study of AuEr dilute alloys

    NASA Astrophysics Data System (ADS)

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

    1981-06-01

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

  5. ESR Study on Irradiated Ascorbic Acid Single Crystal

    SciTech Connect

    Tuner, H.; Korkmaz, M.

    2007-04-23

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

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

    NASA Astrophysics Data System (ADS)

    Kameya, Hiromi; Ukai, Mitsuko; Shimoyama, Yuhei

    2013-03-01

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

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

    SciTech Connect

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

    1985-09-15

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

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

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

  9. ESR studies on hot-wire amorphous silicon

    SciTech Connect

    Unold, T.; Mahan, A.H.

    1997-07-01

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

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

    PubMed

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

    2009-01-30

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

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

    NASA Astrophysics Data System (ADS)

    Kadiiska, Maria B.; Mason, Ronald P.

    2002-04-01

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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    SciTech Connect

    Freed, J.H.

    1980-11-01

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

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

    SciTech Connect

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

    1997-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    SciTech Connect

    Freed, J. H.

    1982-09-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

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

    SciTech Connect

    Kilic, S.; Baysal, B.M.

    1981-12-01

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

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

    SciTech Connect

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

    1987-05-01

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

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

    SciTech Connect

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

    1994-03-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

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

    SciTech Connect

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

    1989-10-11

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

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

    SciTech Connect

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

    1998-08-01

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

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

    NASA Astrophysics Data System (ADS)

    Pugel, D. E.

    2001-03-01

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

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

    PubMed Central

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

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-01-01

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

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

    PubMed

    Kimura, H; Simodate, H; Suzuki, M

    1990-01-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    1990-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    SciTech Connect

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

    1991-03-15

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

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

    PubMed

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

    2016-08-01

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

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

    SciTech Connect

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

    2009-12-04

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

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

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

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

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

    SciTech Connect

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

    1997-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1984-12-01

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

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

    PubMed

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

    2016-06-15

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

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

    PubMed

    Oldfield, F F; Yasuda, H K

    1999-03-15

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

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

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed Central

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

    1988-01-01

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

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

    SciTech Connect

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

    1996-06-01

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

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

    SciTech Connect

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

    1983-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Locher, Sarah E.; Box, Harold C.

    1980-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    PubMed

    Chin, Michael; Somasundaran, Ponisseril

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

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

    PubMed

    Kondo, T; Riesz, P

    1991-07-01

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

  14. 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.

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

    PubMed

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

    2009-11-01

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

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

    SciTech Connect

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

    2012-03-08

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

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

    PubMed Central

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

    2010-01-01

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

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

    PubMed Central

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed Central

    Alfonso, Leopoldo

    2005-01-01

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

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

    SciTech Connect

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

    2011-11-15

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

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

    ERIC Educational Resources Information Center

    Beck, Rainer; Nibler, Joseph W.

    1989-01-01

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

  6. ESR dating of pseudotachylite

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

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

    SciTech Connect

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

    1986-01-01

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

  10. 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.

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

    PubMed

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

    2013-12-15

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

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

    SciTech Connect

    Qin, X.Z.; Williams, F.

    1986-05-22

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

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

    PubMed

    Inoue, M; Utsumi, H; Kirino, Y

    1994-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-12-01

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

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

    PubMed

    Andoh, M

    1989-12-01

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

  16. ESR spectroscopic properties of irradiated gum Arabic.

    PubMed

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

    2013-12-01

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

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

    SciTech Connect

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

    1993-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-09-01

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

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

    PubMed Central

    Bannister, J V; Bannister, W H

    1985-01-01

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

  20. Probing Polymer-Segment Motions By ESR

    NASA Technical Reports Server (NTRS)

    Tsay, Fun-Dow; Gupta, Amitava

    1988-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    SciTech Connect

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

    1992-08-01

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

  4. ESR teleradiology survey: results.

    PubMed

    2016-08-01

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

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

    SciTech Connect

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

    1983-01-15

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

  6. ESR response of gamma-irradiated sulfamethazine

    NASA Astrophysics Data System (ADS)

    Çolak, Seyda; Korkmaz, Mustafa

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed Central

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

    2010-01-01

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

  9. ESR dosimetry for atomic bomb survivors and radiologic technologists

    NASA Astrophysics Data System (ADS)

    Tatsumi-Miyajima, Junko

    1987-06-01

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

  10. ESR (Erythrocyte Sedimentation Rate) Test

    MedlinePlus

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed

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

    2010-09-01

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

  13. ESR identification of gamma-irradiated albendazole

    NASA Astrophysics Data System (ADS)

    Çolak, Seyda

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    SciTech Connect

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

    1986-01-16

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

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

    PubMed

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Okada, Michio; Teraoka, Yuden

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

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

    NASA Astrophysics Data System (ADS)

    Aleksandrova, Olga

    2015-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Aleksandrova, Olga

    2015-04-01

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

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

    PubMed

    Ji, Ming; Ruthstein, Sharon; Saxena, Sunil

    2014-02-18

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

  2. Persistent free radical ESR signals in marine bivalve tissues

    SciTech Connect

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

    1992-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-02-01

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

  4. ESR dating of teeth from Brazilian megafauna

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

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

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

    PubMed

    Chandra, Sulekh; Vandana

    2014-08-14

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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    SciTech Connect

    Makino, K.

    1980-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-05-01

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

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

    ERIC Educational Resources Information Center

    Gordon, Malcolm; And Others

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

  11. Applications of ESR to carbonaceous materials

    SciTech Connect

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

    1982-01-01

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

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

    PubMed Central

    Adhikary, Amitava; Kumar, Anil; Khanduri, Deepti

    2015-01-01

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

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

    PubMed

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

    2016-07-28

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

  14. ESR

    MedlinePlus

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

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

    PubMed

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    SciTech Connect

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

    2010-07-30

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

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

    SciTech Connect

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

    1991-01-01

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

  3. ESR in CVD silicon and silicon-carbon alloys

    NASA Astrophysics Data System (ADS)

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

    1981-03-01

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

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

    PubMed

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

    2015-11-01

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

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

    SciTech Connect

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

    2015-11-07

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

  6. Study of thermal stability of Cu2Se thermoelectric material

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

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

    PubMed

    Maniprasad, Pavithra; Santra, Swadeshmukul

    2012-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  16. Point defect study of CuTi and CuTi sub 2

    SciTech Connect

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

    1991-03-01

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

  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†

    PubMed Central

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

    2016-01-01

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

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

    SciTech Connect

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

    1981-02-19

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

  19. 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.

  20. 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.

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

    NASA Technical Reports Server (NTRS)

    Revcolevschi, A.; Grant, N. J.

    1972-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Brumby, Steven; Yoshida, Hiroyuki

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    PubMed

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

    2015-02-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

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

    SciTech Connect

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

    1999-11-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  10. Transient melting of an ESR electrode

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  11. ESR melting under constant voltage conditions

    SciTech Connect

    Schlienger, M.E.

    1997-02-01

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

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

    PubMed

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

    1996-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

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

    NASA Astrophysics Data System (ADS)

    Olenga, Antoine; Fazleev, N. G.

    2012-10-01

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

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

    PubMed Central

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

    2007-01-01

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

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

    SciTech Connect

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

    2010-12-03

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

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

    PubMed

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

    2015-02-01

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

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

    SciTech Connect

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

    2010-06-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  20. ESR Measurement Of Crystallinity In Semicrystalline Polymers

    NASA Technical Reports Server (NTRS)

    Kim, Soon Sam; Tsay, Fun-Dow

    1989-01-01

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

  1. Educating for Social Responsibility. The ESR Journal.

    ERIC Educational Resources Information Center

    Pittman, Susan Peters, Ed.

    1990-01-01

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

  2. An ESR Investigation of Synthetic Pyrite Crystals

    NASA Astrophysics Data System (ADS)

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

    1989-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    SciTech Connect

    Iliev, I P; Gocheva-Ilieva, S G

    2013-11-30

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

  5. 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.

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

    PubMed

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

    2016-08-01

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

  7. 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.

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed 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

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

    PubMed

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

    2015-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    SciTech Connect

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

    1989-01-12

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

  13. 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

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

    SciTech Connect

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

    1983-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    SciTech Connect

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

    1996-02-10

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  19. 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.

  20. Electrochemical Aspects of the ESR Process

    NASA Astrophysics Data System (ADS)

    Mitchell, Alec

    2016-07-01

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

  1. Pulse Dipolar ESR and Protein Superstructures and Function

    NASA Astrophysics Data System (ADS)

    Freed, Jack

    2014-03-01

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

  2. Characterization of macrosegregation in ESR IN-718

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

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

    PubMed

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

    2014-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    PubMed Central

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

    1985-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Dojčinović, M.

    2011-09-01

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

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

    SciTech Connect

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

    1998-09-04

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

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

    SciTech Connect

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

    2013-02-15

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

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

    NASA Astrophysics Data System (ADS)

    Timms, Christopher

    2015-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

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

  13. Photoluminescence Studies in CuAlS2 Crystals

    NASA Astrophysics Data System (ADS)

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

    1992-08-01

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

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

    PubMed Central

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

    2015-01-01

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

  15. Impact of ESR1 Gene Polymorphisms on Migraine Susceptibility

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1991-03-01

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

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

    SciTech Connect

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

    1999-07-01

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

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

    SciTech Connect

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

    1999-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Yıldırım, İ.; Karabulut, B.

    2016-04-01

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

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

    PubMed

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

    2016-05-25

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

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

    PubMed

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

    2013-09-01

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

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

    SciTech Connect

    Lancione, G.V.

    1982-01-01

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

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  10. ESR Studies of a Reorienting Nickel Complex

    NASA Astrophysics Data System (ADS)

    Kowert, Bruce

    2007-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

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

    SciTech Connect

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

    2015-01-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-12-01

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

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

    SciTech Connect

    Lu, J.; Qiao, G.W.

    1988-01-01

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

  16. Modified Ni-Cu catalysts for ethanol steam reforming

    SciTech Connect

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

    2013-11-13

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

  17. Modified Ni-Cu catalysts for ethanol steam reforming

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

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

    SciTech Connect

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

    1987-12-31

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed Central

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

    2016-01-01

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

  2. 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.

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

    PubMed

    Guilarte, Verónica; Trompier, François; Duval, Mathieu

    2016-01-01

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

  4. 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

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

    NASA Astrophysics Data System (ADS)

    Abo-Elsoud, Mohamed A.

    2015-04-01

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

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

    PubMed Central

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

    2014-01-01

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

  7. Ionosphere and Thermosphere above EISCAT-ESR during IPY

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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