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Sample records for cu esr studies

  1. 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.

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

    SciTech Connect

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

    1986-07-01

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

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

    SciTech Connect

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

    1992-05-10

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

  4. Microwave absorption studies of high T sub c superconductors and related materials 8; ESR of DPPH coated on BiSrCaCuO films fabricated on MgO (100) substrates

    SciTech Connect

    Sugawara, K.; Tanaka, S. )

    1992-06-20

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

  5. ESR, thermoelectrical and positron annihilation Doppler broadening studies of CuZnFe2O4-BaTiO3 composite

    NASA Astrophysics Data System (ADS)

    Hemeda, O. M.; Mahmoud, K. R.; Sharshar, T.; Elsheshtawy, M.; Hamad, Mahmoud A.

    2017-05-01

    Composite materials of Cu0.6Zn0.4Fe2O4 (CZF) and barium titanate (BT) with different concentrations were prepared by high energy ball milling method. The composite samples of CZF and BT were studied using Infrared, ESR and positron annihilation Doppler broadening (PADB) spectroscopy techniques as well as thermo-electric power measurements. The results confirm formation of the composite, and presence of two ferrimagnetic and ferroelectric phases, simultaneously. In addition, Fe-O bond for both tetrahedral and octahedral sites, population and distribution of cations at A and B sites are varied with BT content. The values of resonance field, line width of ESR spectrum and charge carrier concentration increase by increasing BT content. The value of the g factor for our samples with low BT content is greater than g-factor value of the isolated free electron. On the contrary, the g-factor values for samples with high BT content are smaller than the free isolated electron. PADB line-shape S-parameter suggests that there are increases of the density of the delocalized electrons, defect size and concentration caused by highly adding BT phase. In addition, PADB results confirm the homogeneity of composite phases and same structure of defects in BT-CZF composite samples.

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

    NASA Astrophysics Data System (ADS)

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

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

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

    SciTech Connect

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

    1991-06-01

    This paper reports that the electron spin resonances of both DPPH surface coatings and Y{sub 2}Ba{sub 1}Cu{sub 1}O{sub 5} (211 phase) non-superconducting inclusions have been used to probe the flux pinning in high critical current density Y-Ba-Cu-O bulk superconductors prepared by the MPMG (Melt-Powder-Melt-Growth) method. The ESR lineshapes for both the surface coatings and the 211 inclusions were observed to broaden when the MPMG samples entered the superconducting state. The excess ESR linewidth for the DPPH coatings was found to increase monotonically with decreasing temperature, as the result of increasing field gradients due to pinned flux. The ESR linewidth of the 211 inclusions had a complicated temperature dependence. This linewidth was less than that of isolated Y{sub 2}Ba{sub 1}Cu{sub 1}O{sub 5} below 20 K, possibly due to a lower magnetic ordering temperature, mechanical stress, and/or different composition of the inclusions as compared to isolated Y{sub 2}Ba{sub 1}Cu{sub 1}O{sub 5}. Strong hysteresis in the ESR linewidths due to flux trapping was observed at low temperatures. Comparisons with the ESR linewidth of DPPH coated on the surface of the samples suggest that this flux trapping is due to strong pinning in the neighborhood of the 211 inclusions.

  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. Genetic polymorphisms in ESR1 and ESR2 genes, and risk of hypospadias in a multiethnic study population.

    PubMed

    Choudhry, Shweta; Baskin, Laurence S; Lammer, Edward J; Witte, John S; Dasgupta, Sudeshna; Ma, Chen; Surampalli, Abhilasha; Shen, Joel; Shaw, Gary M; Carmichael, Suzan L

    2015-05-01

    Estrogenic endocrine disruptors acting via estrogen receptors α (ESR1) and β (ESR2) have been implicated in the etiology of hypospadias, a common congenital malformation of the male external genitalia. We determined the association of single nucleotide polymorphisms in ESR1 and ESR2 genes with hypospadias in a racially/ethnically diverse study population of California births. We investigated the relationship between hypospadias and 108 ESR1 and 36 ESR2 single nucleotide polymorphisms in 647 cases and 877 population based nonmalformed controls among infants born in selected California counties from 1990 to 2003. Subgroup analyses were performed by race/ethnicity (nonHispanic white and Hispanic subjects) and by hypospadias severity (mild to moderate and severe). Odds ratios for 33 of the 108 ESR1 single nucleotide polymorphisms had p values less than 0.05 (p = 0.05 to 0.007) for risk of hypospadias. However, none of the 36 ESR2 single nucleotide polymorphisms was significantly associated. In stratified analyses the association results were consistent by disease severity but different sets of single nucleotide polymorphisms were significantly associated with hypospadias in nonHispanic white and Hispanic subjects. Due to high linkage disequilibrium across the single nucleotide polymorphisms, haplotype analyses were conducted and identified 6 haplotype blocks in ESR1 gene that had haplotypes significantly associated with an increased risk of hypospadias (OR 1.3 to 1.8, p = 0.04 to 0.00001). Similar to single nucleotide polymorphism analysis, different ESR1 haplotypes were associated with risk of hypospadias in nonHispanic white and Hispanic subjects. No significant haplotype association was observed for ESR2. The data provide evidence that ESR1 single nucleotide polymorphisms and haplotypes influence the risk of hypospadias in white and Hispanic subjects, and warrant further examination in other study populations. Copyright © 2015 American Urological Association

  11. ESR study of the guanine cation

    NASA Astrophysics Data System (ADS)

    Close, David M.; Sagstuen, Einar; Nelson, William H.

    1985-05-01

    It has been proposed that the primary direct radiation damage products in DNA are guanine cations and thymine anions. Experiments reported here characterize a guanine cation observed in a single crystal of guanine:HCl:H2O. ESR experiments were performed by x-irradiating and observing the crystals at 15 K. Spectral parameters for the cation include N3 and N10 hyperfine couplings, a C8-Hα hyperfine coupling, and two small exchangeable couplings presumably from the N10 protons. The computed spin densities of ρ(N3)=0.283, ρ(N10)=0.168, and ρ(C8)=0.182 agree nicely with those observed for the guanine cation in DNA. In the single crystal the native molecule is protonated at N7. It is proposed that once the native molecule is oxidized it rapidly deprotonates at N7 to form the cation observed.

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

    NASA Astrophysics Data System (ADS)

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

    2003-11-01

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

  13. Study of Cleanliness of High Nitrogen Steel in ESR

    NASA Astrophysics Data System (ADS)

    Xuwei, Tang; Rong, Zhu

    This paper compares inclusions in high nitrogen steel before and after ESR process, analyzes the influence of slag systems and total oxygen content in consumable ingots. The total oxygen content is reduced apparently during ESR process, which indicates good effects on removal of inclusions. In the experiment, it shows that different slag systems will affect the result of inclusions removal significantly; proper w(CaO/Al2O3) will reduce the level of inclusions and total oxygen content in ESR ingots. In ESR process, the type and chemical composition of inclusions have no difference when oxygen content in consumable ingots is different, which means O content in consumable ingots have no direct relationship with cleanliness of ESR ingots. In typical inclusions, w(MnO)/w(MnO+Al2O3)≈0.23 0.32. The total oxygen content of ESR ingots keeps between 20 30ppm when the oxygen contents in consumable ingots are diverse from 40 to 100ppm. Meanwhile, this paper studies desulfurization process of high nitrogen steel in ESR, analyzes the influence of slag systems a nd remelting rates on desulfurization efficiency. The results indicate that the average size and quant ity of sulfide inclusion decrease after ESR process. The typical inclusion after ESR process is MnS+Al2O3. Slag system with proper CaO content has higher sulfur partition ratio, which leads to better desulfurization effect. The desulfurization rate changes greatly with different remelting rates, which indicates the kinetic parameter has more influence in desulfurization. The reason of this phenomenon is that the process of desulfurization can be considered as a non-equilibrium reaction, which differs with thermodynamic equilibrium. In kinetic study, it is founded that the desulfurization efficiency increases with higher remelting area, sulfur partition and lower remelting rate, which is different from experiment. The desulfurization efficiency decreases firstly and then recovers when remelting rate drops. The

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Korkmaz, Güney; Polat, Mustafa; Korkmaz, Mustafa

    2010-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Shin, Byong-Kyu; Saxena, Sunil

    2009-03-01

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

  17. 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.

  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. ESR/spin probe study of ice cream.

    PubMed

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

    2006-07-12

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

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

    PubMed

    Singh, Vinod P

    2008-11-01

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

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

    SciTech Connect

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

    1995-10-25

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

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  6. CW ESR studies of impurity-helium condensates containing krypton and hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Järvinen, J.; Bernard, E. P.; Boltnev, R. E.; Khmelenko, V. V.; Lee, D. M.

    2009-02-01

    Impurity-Helium condensates (IHCs) containing krypton and hydrogen atoms have been studied in superfluid helium-4 via CW ESR techniques. The IHCs studied in this work are gel-like aggregates of nanoclusters composed of krypton and hydrogen atoms. We have found that such samples contain very high average concentrations of hydrogen atoms (~1018cm-3) as obtained by integration of the microwave absorption signal. Local concentrations (~1019cm-3) of H atoms were calculated from the ESR line width. Detailed studies of the ESR line shapes lead to the conclusion that a large fraction of the H atoms lies on the krypton cluster surfaces.

  7. Metabolism of carbon tetrachloride to trichloromethyl radical: An ESR and HPLC-EC study.

    PubMed

    Stoyanovsky, D A; Cederbaum, A I

    1999-08-01

    Extensive ESR spin-trapping studies with alpha-phenyl-N-tert-butylnitrone (PBN) have shown that carbon tetrachloride (CCl(4)) is metabolized to trichloromethyl radical ((*)CCl(3)). However, the ESR analysis of alpha-phenyl-N-tert-butylnitrone (PBN)-spin trapped (*)CCl(3) in biological systems appears to be complicated. It has been reported that after in vivo administration of PBN and CCl(4) to rats, most of the PBN-CCl(3) adduct collected in the bile was ESR silent, suggesting reduction of the nitroxide to its hydroxylamine form. The PBN-CCl(3) nitroxide was also shown to undergo a NADPH-dependent reduction in the presence of liver microsomes. Thus, it appears that the variability (or the absence) of the ESR signal of PBN-CCl(3) nitroxide in biological systems reflects, at least in part, the fluctuations in the equilibrium between the nitroxide and hydroxylamine forms of this adduct. To test this possibility, ESR and HPLC experiments with electrochemical detection (EC) were conducted for analysis of the major redox form of the PBN-CCl(3) adduct in vivo. Standard procedures for the in vitro preparation of both redox forms of PBN-CCl(3) and for their HPLC-EC analysis and electrochemical profiles were established. The intensity of the initially observed ESR spectrum of PBN-CCl(3) nitroxide of the liver extract from a CCl(4)- and PBN-treated rat was relatively constant; after an addition of K(3)[Fe(CN)(6)] to the extract, the intensity of the ESR spectrum increased by 1 order of magnitude, most likely due to the co-oxidation of ESR silent PBN-derived hydroxylamines. The addition of PBN-CCl(3) nitroxide to the liver homogenate resulted in the rapid loss of the ESR signal. The HPLC-EC analysis of the liver extract revealed that the in vivo spin trapping of (*)CCl(3) with PBN leads to a preferential formation of the ESR silent PBN-CCl(3) hydroxylamine. The predominant presence of the hydroxylamine derivative was also detected in the blood of a CCl(4)-treated rat. The

  8. IN SITU optical and ESR studies of polyazulene

    NASA Astrophysics Data System (ADS)

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

    1986-11-01

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

  9. 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.

  10. ESR Study on Irradiated Ascorbic Acid Single Crystal

    NASA Astrophysics Data System (ADS)

    Tuner, H.; Korkmaz, M.

    2007-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Kumar, B. Vijaya; Vithal, M.

    2012-06-01

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

  12. 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.

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

    PubMed

    Kasumov, Veli T; Köksal, Fevzi

    2012-12-01

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

  14. Magnetic interactions between Gd ions in Gd xY 1- xBa 2Cu 3O 7-δ: An ESR investigation

    NASA Astrophysics Data System (ADS)

    Filip, C.; Kessler, C.; Balibanu, F.; Kleeman, P.; Darabont, A.; Giurgiu, L. V.; Mehring, M.

    1996-05-01

    We analyse the ESR line width of Gd in Gd xY 1- xBa 2Cu 3O 7-δ as a function of the Gd concentration x and temperature in the normal state. The powder samples were oriented in a magnetic field of 7 T. An orientation dependence of the line width was found. The experimentally observed change of the ESR line width with Gd concentration x is compared with a model calculation based on the Gd-spin dipole-dipole and exchange interaction. The absence of resolved fine-structure splitting is explained by a dominance of the dipole-dipole and exchange interaction.

  15. 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.

  16. 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.%.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  18. Correlation between erythrocyte sedimentation rate (ESR) dynamics and blood luminescence studied using optoelectronic devices

    NASA Astrophysics Data System (ADS)

    Novikov, Cyril N.; Bouravleva, Ekaterina V.; Fadyukova, Olga E.; Voeikov, Vladimir V.; Koshelev, Vladimir B.

    2003-10-01

    Simultaneous temporal analysis of whole human or rat blood luminescence and erythrocytes sedimentation rate (ESR) in same blood using special computerized optoelectronic devices for single photon counting and for high temporal resolution of the rate of sedimentation of red blood/plasma boundary revealed correlation between both time series. Correlation was observed in vitro in normal blood, after action of physical (height of blood column) and of chemical (hydrogen peroxide) factors, and in experimental cerebral ischemia. An ischemia was invoked in rats by occlusion of both common carotid arteries. ESR was studied with the device "ESR-scan" and the dynamics of respiratory burst (RB) by a luminol-dependent luminescence method on the same blood samples. There was a noticeable increase of intensity of RB in whole rat blood and significant acceleration of ESR in blood diluted on 50% in 90 minutes after applying a ligature on carotid arteries. The individual differences between animals attesting to different degree of RB and ESR activation in blood both in intact animals and after operational intervention was obtained. Revealed correlation points to considerable relation between blood energy and its mechanical properties.

  19. ESR and dielectric studies on superparamagnetic LaFeO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Kumar, A. Sendil; Bhatnagar, Anil K.

    2017-05-01

    Superparamagnetic LaFeO3 nanoparticles are synthesized through sol gel method. Structural, magnetic and dielectric studies are carried out. Temperature dependent ESR studies show that the intensity of the ESR spectra increases at higher temperatures. The line shape at low temperature has inhomogeneous broadening and at higher temperature more symmetry is developed and it fits better with the Lorentzian. Resonance field decreases when temperature is lowered due to dipolar interactions and there are no extrema in linewidth are observed. Single semi-circular arc in the Cole-Cole plot shows that the AC conductivity is from grains only.

  20. 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.

  1. 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.

  2. Multifrequency ESR study of spin labeled molecules in inclusion compounds with cyclodextrins

    PubMed Central

    Dzikovski, Boris; Tipikin, Dmitriy; Livshits, Vsevolod; Earle, Keith; Freed, Jack

    2009-01-01

    The molecular dynamics of spin labeled compounds included into the solid phase of cyclodextrins (CD) has been studied using conventional (X-Band) ESR at 9 GHz and high-field high-frequency (HFHF) ESR at 240 and 170GHz. The patterns of axial rotation at these higher frequencies are clear just by inspection of the spectrum, unlike the case for 9 GHz spectra. That is HFHF ESR is sensitive to molecular motion about the diffusion axis collinear with the X, Y or Z-direction of the magnetic g- and A-tensors of the nitroxide moiety (referred to respectively as X, Y or Z-rotation). For doxyl stearic acids (Z-rotation) and TEMPOyl caprylate (X-rotation) included in β- and γ-CD’s we were able to determine the rate of molecular motion and the corresponding potential barriers. We emphasize that determining the rate of Z-rotation by ESR is feasible only using HFHF ESR. For the X-rotation case we suggest that the motion of the nitroxide moiety consists of fast small-angle librations about the magnetic X-axis superimposed by rotational diffusion about the same axis. The potential barrier of 1.7 Kcal/mol for this rotational diffusion is unusually low. A fascinating feature of TEMPO derivatives included in β-CD is the detectable molecular motion at temperatures below 77K. For the other CD – spin probe systems, we used multifrequency analysis to assign the conformations of spin-labeled molecules. A dramatic spectral change for 16-sasl in β- and γ-CDs at ~ 260K corresponds to a tilting of the position of the nitroxide moiety on the rotating molecule relative to the long diffusion axis, while for TEMPO derivatives in γ cyclodextrin below 200K, we observe a rapid transition from fast to very slow rotational motion. More complex features are best studied by means of multifrequency ESR experiments. The visual clarity and the simplicity of analysis of the ESR spectra shown in this work should provide a benchmark for future studies of molecular motion by HFHF ESR. PMID:19639141

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

    PubMed

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

    1984-01-01

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

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

  6. 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

  7. 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.

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

    PubMed

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

    1999-04-01

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

  9. ENDOR and ESR studies of a stable radical in irradiated cytidine

    NASA Technical Reports Server (NTRS)

    Allison, D. L.; Alexander, C., Jr.

    1974-01-01

    A model is proposed for a stable radical species formed by X-irradiation in a single crystal of cytidine and studied by electron nuclear double resonance (ENDOR) and electron spin resonance (ESR) techniques at room temperature. ENDOR and ESR spectra are analyzed to obtain the principal values of the spectroscopic splitting factor and the spectroscopic and hyperfine splitting tensors. The results show hyperfine coupling of an unpaired electron to one hydrogen nucleus and two slightly different geometric forms of the radical with small differences in hyperfine couplings. It is proposed that this radical is formed in the ribose sugar group with a hydrogen atom in a beta position coupling with respect to a carbon-centered unpaired electron and a spin density of approximately 0.2 on a carbon atom.

  10. 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.

  11. 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

  12. ESR studies and dating of Egyptian gypsum at Ras Mala'ab, Sinai, Egypt

    NASA Astrophysics Data System (ADS)

    Abdel-Monem, A. A.; Abdel-Razek, Y. A.; Hassan, G. M.; Eissa, H. M.; Rasheed, N. M.; Morsy, M.

    2010-01-01

    A gypsum sample from the famous gypsum-anhydrite evaporitic deposit composing the Ras Mala'ab Formation, Upper Miocene, occurring at Ras Mala'ab, on the east coast of the Gulf of Suez, was subjected to electron spin resonance (ESR) dosimetric studies. ESR was further used to date the formation or most recent recrystallization of the gypsum. The gypsum derivative ESR spectrum is characterized by the large broad Fe2+ signal (g=2.50) and hf-sixtet Mn2+ signals. Only the characteristic gypsum signal (G1, g=2.0040) was detected between the third and fourth lines of the hf-Mn2+ which is attributed to the electron-center SO ? . This signal was sensitive to artificial γ-irradiation and showed significant enhancement using a γ-dose of 550 Gy. Additionally, the signal was very stable up to 400 °C. The gypsum sample with a total dose of 1500 Gy, determined graphically by extrapolating the linear relationship between defect concentration and the artificial γ-doses for (G1, g=2.0040) and an annual dose (D) due to cosmic rays (0.3 mGy), yielded an age of 5.00 Ma. This could mean the age of formation or latest recrystallization of this gypsum deposit. The geological age assignment of the Ras Mala'ab Group, including the evaporitic gypsum unit, is Middle to Late Miocene. It is directly overlain by the Pliocene clastics at the locality of Ras Mala'ab. This might suggest that these evaporitic gypsum facies represent the top of the Serravallian (mid-late) Miocene in the Gulf of Suez area. Since the Serravallian period was between 14.8 and 11.2 Ma ago; therefore, the ESR age of the Ras Mala'ab gypsum represents the latest recrystallization event of these gypsum deposits.

  13. Studies on lipid membranes by two-dimensional Fourier transform ESR: Enhancement of resolution to ordering and dynamics.

    PubMed Central

    Crepeau, R H; Saxena, S; Lee, S; Patyal, B; Freed, J H

    1994-01-01

    The first two-dimensional Fourier-transform electron spin resonance (2D-FT-ESR) studies of nitroxide-labeled lipids in membrane vesicles are reported. The considerable enhancement this experiment provides for extracting rotational and translational diffusion rates, as well as orientational ordering parameters by means of ESR spectroscopy, is demonstrated. The 2D spectral analysis is achieved using theoretical simulations that are fit to experiments by an efficient and automated nonlinear least squares approach. These methods are applied to dispersions of 1-palmitoyl-2oleoyl-sn-glycerophosphatidylcholine (POPC) model membranes utilizing spin labels 1-palmitoyl-2-(16-doxyl stearoyl) phosphatidylcholine and the 3-doxyl derivative of cholestan-3-one (CSL). Generally favorable agreement is obtained between the results obtained by 2D-FT-ESR on vesicles with the previous results on similar systems studied by continuous wave (cw) ESR on aligned samples. The precision in determining the dynamic and ordering parameters is significantly better for 2D-FT-ESR, even though the cw ESR spectra from membrane vesicles are resolved more poorly than those from well aligned samples. Some small differences in results by the two methods are discussed in terms of limitations of the methods and/or theoretical models, as well as possible differences between dynamic molecular structure in vesicles versus aligned membranes. An interesting observation with CSL/POPC, that the apparent homogeneous linewidths seem to increase in "real time," is tentatively attributed to the effects of slow director fluctuations in the membrane vesicles. PMID:8061198

  14. Pulse ESR studies of impurity-helium condensates containing Kr, H, and D atoms

    NASA Astrophysics Data System (ADS)

    Bernard, E. P.; Khmelenko, V. V.; Lee, D. M.

    2009-02-01

    Hydrogen and deuterium atoms trapped in impurity-helium condensates (IHCs) formed by condensing krypton, hydrogen, and deuterium atoms in superfluid 4He were studied with pulse electron spin resonance. We have used electron spin echo envelope modulation (ESEEM) to probe the magnetic interactions between atoms of hydrogen isotopes and 83Kr nuclei. Modeling of the ESEEM spectra suggests that the vast majority of the hydrogen and deuterium atoms reside at the surface of the Kr clusters. This conclusion is in agreement with that from continuous wave ESR experiments with IHCs of similar composition.

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

    NASA Astrophysics Data System (ADS)

    Das, Ranjan; Prabhananda, B. S.

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

  16. Applications of ESR dating and18O Paleotemperature data for studies on Quaternary sea-level changes

    NASA Astrophysics Data System (ADS)

    Huang, Peihua; Peng, Zicheng; Jin, Sizhao; Liang, Renyou; Quan, Yucai; Wang, Zhaorong

    1989-03-01

    Electron Spin Resonance (ESR) dating is a relatively new technique applicable also to the dating of materials from littoral zones and shallow sea regions, such as shells, corals, bones and teeth, foraminifera, diatoms, etc. ESR dating can span the time interval between the older limit of14C dating and the younger limit of the K-Ar dating, an interval of 103 106 years. Therefore, ESR technique is very suitatie for the measurement of the age of Quaternary sea—level changes. This paper gives some samples’ results by ESR dating from Early Pleistoncene to Holocene. The Quaternary sea—level changes in China were mainly eustatisms that corresponded to the paleotemperature variation. We have just begun study on the18O Paleotemperature in our continental area. Preliminary results show the temperature curve of the stalagmitic growth in caves corresponds well to the sea—level changes in 76 55×103 years B. P. ESR dating and studies of the18O Paleotemperature in East China will raise studies on Quaternary sea—level changes to a higher scientific basis.

  17. ESR study of the direct radiolysis of DNA, DNA-histones and DNA-intercalators complexes

    NASA Astrophysics Data System (ADS)

    Faucitano, A.; Buttafava, A.; Martinotti, F.; Pedraly-Noy, G.

    The nature of the radicals contributing to the room temperature spectrum of irradiated "dry" DNA, with special reference to the central structure, is discussed, and the thesis of their ionic origin tested by irradiation experiments with intercalators. The mechanism of spin transfer protein→DNA has been investigated through a comparative ESR study on the DNA-histones complex, the structureless random molecular mixture of the DNA-histones and the neat components. The yield of spin transfer is enhanced in the random mixture, presumably because of the greater efficiency of molecular contacts. Evidence of the scavenging of electrons by the thymine and cytosine bases, as a key mechanism for the spin transfer, has been obtained.

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

    PubMed

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

    1999-08-16

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-12-01

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

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

    PubMed

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

    2009-09-01

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

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

    PubMed

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

    2000-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2004-06-01

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

  3. 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.

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

    SciTech Connect

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

    1984-03-01

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

  5. 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

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

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

    PubMed

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

    2009-04-23

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

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    NASA Astrophysics Data System (ADS)

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

    2004-04-01

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

  11. ESR study of molecular orientation and dynamics of nitronyl nitroxide radicals in CLPOT 1D nanochannels.

    PubMed

    Kobayashi, Hirokazu; Morinaga, Yuka; Fujimori, Etsuko; Asaji, Tetsuo

    2014-07-10

    New inclusion compounds (ICs) were prepared using the organic 1D nanochannels of 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) as a nanosized template and nitronyl nitroxide (NN) radicals such as phenylnitronylnitroxide (PhNN) and p-nitrophenylnitronylnitroxide (p-NPNN). ESR measurements below 255 K for the CLPOT ICs diluted with spacer molecules gave rigid limit spectra similar to that for PhNN molecules in a glassy ethanol matrix at low temperature, which suggests isolation of the radical molecules. ESR measurements for them in the range of 290-400 K gave a modulated quintet ESR signal, which suggested uniaxial rotational diffusion of NN radicals in the nanochannels approximately around the principal y-axis of the g-tensors. In the ESR measurements to 430 K for the [(CLPOT)2-(p-NPNN)0.07] IC without spacers, the broader line width than the case in dilution was observed by inter-radical dipolar interaction. In every case, the rotational diffusion activation energies of NN radicals in the CLPOT nanochannels were several times larger than those of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical derivatives (4-X-TEMPO) in CLPOT nanochannels. This is expected due to the larger molecular size of NN radicals than 4-X-TEMPO or stronger interaction between NN radicals and the surrounding host or guest molecules.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    SciTech Connect

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

    2016-05-23

    Electron spin resonance (ESR) studies were carried out for 2mM {sup 14}N labeled {sup 2}H 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. Cu(II) complexes in bacterial growth medium: electron spin resonance study

    NASA Astrophysics Data System (ADS)

    Jung, Katinka; Ristori, Sandra; Martini, Giacomo

    2000-02-01

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

  17. ESR and optical study of Mn 2+-doped sodium hydrogen orthophosphate dihydrate

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Singh, D. K.

    2008-03-01

    ESR study of Mn 2+-doped sodium hydrogen orthophosphate dihydrate (SHOD) single crystals is done at room temperature. The Mn 2+ spin-Hamiltonian parameters have been evaluated employing a large number of resonant line positions observed for different orientations of the external magnetic field. The values of g, A, B, D, E and a are: 2.0042 ± 0.0002, 86 ± 2 × 10 -4 cm -1, 83 ± 2 × 10 -4 cm -1, 238 ± 2 × 10 -4 cm -1, 76 ± 2 × 10 -4 cm -1, 13 ± 1 × 10 -4 cm -1 for site I and 2.0032 ± 0.0002, 86 ± 2 × 10 -4 cm -1, 83 ± 2 × 10 -4 cm -1, 238 ± 2 × 10 -4 cm -1, 76 ± 2 × 10 -4 cm -1, 13 ± 1 × 10 -4 cm -1 for site II, respectively. The optical absorption study of the crystal is also done. The observed bands are assigned as transitions from the 6A 1g(S) ground state to various excited quartet levels of a Mn 2+ ion in a cubic crystalline field. These bands are fitted with four parameters B, C, Dq and α and the values found for the parameters are B = 777 cm -1, C = 3073 cm -1, Dq = 755 cm -1, and α = 76 cm -1. On the basis of the data obtained the surrounding crystalline field and the nature of metal-ligand bonding are discussed.

  18. 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.

  19. Association study of the estrogen receptor I gene (ESR1) in anorexia nervosa and eating disorders: no replication found.

    PubMed

    Slof-Op 't Landt, Margarita C T; van Furth, Eric F; Meulenbelt, Ingrid; Bartels, Meike; Hottenga, Jouke Jan; Slagboom, P Eline; Boomsma, Dorret I

    2014-03-01

    The female preponderance and onset around puberty in the majority of eating disorders (EDs) suggest that sex hormones, like estrogens, may be involved in the onset of these disorders. An eight-SNP haplotype at the estrogen receptor I (ESR1) gene was found to be associated with anorexia nervosa (AN) (Versini et al., Neuropsychopharmacology, 35, 1818-1825, 2010) and three SNPs from this haplotype (rs726281, rs2295193, and rs3798577) were associated with AN and/or EDs. Our objective was to replicate these findings in an independent cohort of 520 patients with an eating disorder, of whom 244 had AN (142 restricting type) from the GenED study and 2,810 random women from the Netherlands Twin Registry. The frequencies of the eight-SNP haplotype and three ESR1 SNPs were compared between patients with an eating disorder, with AN (restricting type), with bulimia nervosa (BN), and the control women. Neither the haplotype nor the three ESR1 SNPs were associated with EDs, BN, AN, or restricting type AN. Despite sufficient statistical power, the associations reported by Versini et al. (Neuropsychopharmacology, 35, 1818-1825, 2010) were not replicated. Copyright © 2013 Wiley Periodicals, Inc.

  20. 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).

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  2. 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.

  3. 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.

  4. Stabilization of alkane radical-cations, their transport and capture under low temperature irradiation of solutions. Study by the OD ESR technique

    NASA Astrophysics Data System (ADS)

    Tadjikov, B. M.; Melekhov, V. I.; Anisimov, O. A.; Molin, Yu. N.

    The spectra of stabilized solvent holes were obtained by the method of optically detected ESR (OD ESR) in glassy matrices at 77 K. Using this technique we obtained the spectra for radical-cations of cis-decalin, squalene, 2-methylpentane, 3-methylpentane, 3,3-dimethylpentane, 3-methylheptane and 2,3-dimethylbutane. For all matrices except that of squalene, an hf-structure in the OD ESR spectra belonging to the radical-cations of matrices used is detected. Thus an unpaired electron is shown to be localized mainly on one molecule. The efficiency of hole transfer to acceptors with a lower ionization potential is studied in squalene and cis-decalin. It increases with difference in ionization Δ > 0.3 eV. The data on positive charge transfer provided by the OD ESR technique in the present paper, testify in favour of the long range single step tunneling.

  5. Production of superoxide in chloroplast thylakoid membranes ESR study with cyclic hydroxylamines of different lipophilicity.

    PubMed

    Kozuleva, Marina; Klenina, Irina; Proskuryakov, Ivan; Kirilyuk, Igor; Ivanov, Boris

    2011-04-06

    Accumulation of nitroxide radicals, DCP· or TMT·, under illumination of a thylakoid suspension containing either hydrophilic, DCP-H, or lipophilic, TMT-H, cyclic hydroxylamines that have high rate constants of the reaction with superoxide radicals, was measured using ESR. A slower accumulation of TMT· in contrast with DCP· accumulation was explained by re-reduction of TMT· by the carriers of the photosynthetic electron transport chain within the membrane. Superoxide dismutase suppressed TMT· accumulation to a lesser extent than DCP· accumulation. The data are interpreted as evidencing the production of intramembrane superoxide in thylakoids. Copyright © 2011 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  6. A study of optical and ESR radiation-induced absorptions in TeO2 single crystals

    NASA Astrophysics Data System (ADS)

    Kappers, L. A.; Gilliam, O. R.; Bartram, R. H.; Földv&Ári, I.; Watterich, A.

    Gamma-ray and 1.5-MeV electron irradiations are employed in the temperature range 25-175°C to produce radiation effects in undoped paratellurite (α-TeO2) single crystals. Optical absorption and ESR techniques are used to study the growth and annealing of point defects, and spectroscopic observations by these two methods are compared. Pulseannealing experiments are reported over the range 100-500°C. The TeO2 crystal shows much more susceptibility to radiation damage at the higher irradiation temperatures.

  7. ESR Study of Interfacial Hydration Layers of Polypeptides in Water-Filled Nanochannels and in Vitrified Bulk Solvents

    PubMed Central

    Lai, Yei-Chen; Chen, Yi-Fan; Chiang, Yun-Wei

    2013-01-01

    There is considerable evidence for the essential role of surface water in protein function and structure. However, it is unclear to what extent the hydration water and protein are coupled and interact with each other. Here, we show by ESR experiments (cw, DEER, ESEEM, and ESE techniques) with spin-labeling and nanoconfinement techniques that the vitrified hydration layers can be evidently recognized in the ESR spectra, providing nanoscale understanding for the biological interfacial water. Two peptides of different secondary structures and lengths are studied in vitrified bulk solvents and in water-filled nanochannels of different pore diameter (6.1∼7.6 nm). The existence of surface hydration and bulk shells are demonstrated. Water in the immediate vicinity of the nitroxide label (within the van der Waals contacts, ∼0.35 nm) at the water-peptide interface is verified to be non-crystalline at 50 K, and the water accessibility changes little with the nanochannel dimension. Nevertheless, this water accessibility for the nanochannel cases is only half the value for the bulk solvent, even though the peptide structures remain largely the same as those immersed in the bulk solvents. On the other hand, the hydration density in the range of ∼2 nm from the nitroxide spin increases substantially with decreasing pore size, as the density for the largest pore size (7.6 nm) is comparable to that for the bulk solvent. The results demonstrate that while the peptides are confined but structurally unaltered in the nanochannels, their surrounding water exhibits density heterogeneity along the peptide surface normal. The causes and implications, especially those involving the interactions between the first hydration water and peptides, of these observations are discussed. Spin-label ESR techniques are proven useful for studying the structure and influences of interfacial hydration. PMID:23840841

  8. [Optical and ESR-spectroscopic study of electronic adducts of oxymyoglobin and oxyhemoglobin].

    PubMed

    Davydov, R M

    1980-01-01

    It has been shown that low temperatures (77 degrees K) irradiation of frozen water-glycerol solutions of oxymyoglobin and oxyhemoglobin induces kinetically stabilized nonequilibrium electronic adducts (MbO2-, HbO2-) at the expense of binding of thermolyzed electrons formed during matrix radiolysis to oxygenated hem iron. The absorption spectra of HbO2-and MbO2- have a wide band with the maximum at 545 nm and Soret's band at 421 nm. At 77 K MbO2- gives the ESR spectrum with g beta 1 = 2.203 and g beta 2 = 2.103. Unlike the latter HbO2- ESR spectrum consists of two signals g beta 1 = 2.234, g beta 2 = 2.135 and g alpha 1 = 2.195, g alpha 2 = 2.103. Two signals in HbO2- spectra are shown to be conditioned by electronic adducts of oxygenated alpha- and beta-subunits. The observed effect points to non-equivalency of O2 in alpha- and beta-subunits of oxyhemoglobin. Binding of inositolhexaphopshate to oxyhemoglobin induces changes in the electron structure of HbO2-active centres.

  9. 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.

  10. ESR dosimetry using inorganic materials: a case study of Li2CO3 and CaSO4:Dy as prospective dosimeters.

    PubMed

    Murali, S; Natarajan, V; Venkataramani, R; Pushparaja; Sastry, M D

    2001-08-01

    The CO2- radical ion, detected by ESR technique in bones and teeth enamel, was proved to be invaluable in high level and retrospective dosimetry. In these matrices, impurity carbonate (at phosphate sites) was the precursor to CO2-. With a view to investigate the possibility of using inorganic materials such as lithium carbonate as ESR dosimeters, studies were carried out on gamma-irradiated Li2CO3. The intensity of radiation-induced ESR signals of Li2CO3 at g = 2.0036 (CO3-) and g = 2.0006 (CO2-) was followed as a function of gamma dose in the low dose range of 1-1350 Gy. It was observed that the intensity of the ESR signal at g = 2.0036 (CO3-) was in a linear relation with the radiation dose in the dose range 10-800 Gy and the signal at g = 2.0006 (CO2-) showed linear response in the dose range 5-800 Gy. The lowest dose that could be detected in the present studies using the signal of CO2- in Li2CO3 powder samples (approximately 50 mg) is 3.2 Gy. ESR studies were also carried out on the widely used TL dosimetric material CaSO4:Dy and in pure CaSO4 after gamma irradiation. The TL materials were used in powder as well as pellet forms. The linearity of ESR response with dose for powder and pellet forms of CaSO4: Dy was also studied using the signals at g = 2.0030 (SO3-) and at g = 2.0139 (SO4-). It was observed that the range of linearity of dose response extended between 20 and 1200 Gy, for SO3- signals. The results of dosimetric study indicate that the ESR-Li2CO3 system could be used in dosimetric applications in radiotherapy. However, for the actual applications further advancement is needed to lower the detection limit. The TL phosphor, CaSO4:Dy in powder and pellet forms, could be used as ESR dosimeter in the dose range 20-600 Gy.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-07-01

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

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

    PubMed

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

    2015-10-01

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

  14. 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.

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

    PubMed

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

    2011-10-01

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

  16. ESR, electrochemical and cyclodextrin-inclusion studies of triazolopyridyl pyridyl ketones and dipyridyl ketones derivatives.

    PubMed

    Olea-Azar, C; Abarca, B; Norambuena, E; Opazo, L; Jullian, C; Valencia, S; Ballesteros, R; Chadlaoui, M

    2008-11-15

    The electron spin resonance (ESR) spectra of free radicals obtained by electrolytic reduction of triazolopyridyl pyridyl ketones and dipyridyl ketones derivatives were measured in dimethylsulfoxide (DMSO). The hyperfine patterns indicate that the spin density delocalization is dependent of the rings presented in the molecule. The electrochemistry of these compounds was characterized using cyclic voltammetry, in DMSO as solvent. When one carbonyl is present in the molecule one step in the reduction mechanism was observed while two carbonyl are present two steps were detected. The first wave was assigned to the generation of the correspondent free radical species, and the second wave was assigned to the dianion derivatives. The phase-solubility measurements indicated an interaction between molecules selected and cyclodextrins in water. These inclusion complexes are 1:1 with betaCD, and HP-betaCD. The values of Ks showed a different kind of complexes depending on which rings are included. AM1 and DFT calculations were performed to obtain the optimized geometries, theoretical hyperfine constants, and spin distributions, respectively. The theoretical results are in complete agreement with the experimental ones.

  17. ESR study of free radicals in UHMW-PE fiber irradiated by gamma rays

    NASA Astrophysics Data System (ADS)

    Zhao, Yanning; Wang, Mouhua; Tang, Zhongfeng; Wu, Guozhong

    2010-04-01

    ESR spectra of the trapped radicals in an ultra-high molecular weight polyethylene (UHMW-PE) fiber irradiated by gamma rays showed well-resolved hyperfine splitting at room temperature since the c-axis of the crystallites is aligned with the fiber direction and the radicals are trapped in crystallites. The alkyl radical (-CH 2- •CH-CH 2-) was the major product after irradiation in vacuum and in air at room temperature. Some of the alkyl radicals converted to allyl radicals (-CH 2- •CH-CH=CH-) and polyenyl radicals (-CH 2- •CH-(CH=CH) n-CH 2-) during storage in vacuum. Upon storage in air atmosphere, the alkyl radicals decayed by reaction with oxygen. Of particular interest is the very slow decay rate of the alkyl radical trapped in UHMW-PE fiber, the half-life is 26 days in vacuum, and 13 days in air at room temperature, which is about 1/30 and 1/100 of that reported for high density polyethylene (HDPE), respectively. The extremely long lifetime of the alkyl radical is supposed to be caused by the large size of crystallites in UHMW-PE fiber. The rate of radical decay was accelerated by annealing at elevated temperature.

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

    SciTech Connect

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

    1990-01-01

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

  19. 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.

  20. In situ ESR and UV/vis spectroelectrochemical study of eosin Y upon reduction with and without Zn(II) ions.

    PubMed

    Goux, A; Pauporté, T; Lincot, D; Dunsch, L

    2007-04-23

    The electroreduction of eosin Y on a platinum electrode in deaerated slightly acidic aqueous 0.1 mol L(-1) potassium chloride medium is followed in situ by electron spin resonance (ESR) spectroscopy and UV/Vis spectroscopy. The electrochemical formation of a semiquinone radical is proved by both the appearance of an absorbing band at 408 nm, and a strong ESR signal observed during a negative-going scan. The system is also studied in the presence of Zn(II) ions due to its importance for understanding the growth mechanism of nanostructured ZnO/Eosin Y hybrid films by electrodeposition; under such conditions the ESR and UV/Vis response of the semiquinone radical is not observed. Zinc (II) ions form a complex with the dye, which is reduced by a fast two-electron process.

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

    PubMed

    Simon, Ferenc; Murányi, Ferenc

    2005-04-01

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

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

    PubMed

    Tseng, S S; Chang, S

    1975-01-01

    Electron spin resonance spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 absorbed on silica gel at -170C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, re-irradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and which was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals by means of (1) photodissociation of H2O physically adsorbed on the silica gel, or (2) absorption of the excitation energy by the silica gel surface with subsequent cleavage of the silanol bonds, or (3) dissociation of H2O molecules throug photosensitization by the surfaces or a combination of (1) to (3). Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precsursors of formic acid. Our results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth and on dust grains in the interstellar medium.

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

    SciTech Connect

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

    1995-01-01

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

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

    DTIC Science & Technology

    1990-02-01

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

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

    PubMed

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

    2005-04-01

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

  6. Hepatic reduction of carbamoyl-PROXYL in ferric nitrilotriacetate induced iron overloaded mice: an in vivo ESR study.

    PubMed

    Morales, Noppawan Phumala; Yamaguchi, Yumiko; Murakami, Kimiyo; Kosem, Nuttavut; Utsumi, Hideo

    2012-01-01

    Reduction of a nitroxyl radical, carbamoyl-PROXYL in association of free radical production and hepatic glutathione (GSH) was investigated in iron overloaded mice using an in vivo L-band electron spin resonance (ESR) spectrometer. Significant increases in hepatic iron, lipid peroxidation and decrease in hepatic GSH were observed in mice intraperitoneally (i.p.) administrated with ferric nitrilotriacetate (Fe(III)-NTA, a total 45 µmol/mouse over a period of 3 weeks). Free radical production in iron overloaded mice was evidenced by significantly enhanced rate constant of ESR signal decay of carbamoyl-PROXYL, which was slightly reduced by treatment with iron chelator, deferoxamine. Moreover, the rate constant of ESR signal decay was negatively correlated with hepatic GSH level (r=-0.586, p<0.001). On the other hand, hepatic GSH-depletion (>80%) in mice through daily i.p. injection and drinking water supplementation of L-buthionine-[S,R]-sulfoximine (BSO) significantly retarded ESR signal decay, while there were no changes in serum aspartate aminotransferase and liver thiobarbituric acid-reactive substances levels. In conclusion, GSH plays two distinguish roles on ESR signal decay of carbamoyl-PROXYL, as an antioxidant and as a reducing agent, dependently on its concentration. Therefore, it should be taken into account in the interpretation of free radical production in each specific experimental setting.

  7. 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

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

    NASA Astrophysics Data System (ADS)

    Pelluri, Sandhya Rani; Singh, Rajender

    2016-11-01

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

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

    PubMed

    Chikvaidze, E; Khachatryan, I

    2011-08-01

    The ESR spectra of melanin's free radicals in natural black and red hair have been investigated. It is shown that the ESR spectrum of black hair is slightly asymmetric singlet with g=2.0037 and ΔH=0.5 mTl. The ESR spectrum of red hair with g=2.0053 differs from the spectrum of black hair. Using the method of saturation was shown that ESR spectrum of red hair represents a superposition of two signals: a singlet, relating to the black hair, and a triplet from red hair's pheomelanin. Under the influence of visible light (blue with λ(max) =450 nm, green with λ(max) =510 nm and red with λ(max) =650 nm) in both types of hair (black and red), the photoinduced free radicals appear, which indicates an increase in the intensity of already existing ESR spectrum of hair. It should be noted that the ESR spectra of red hair from various donors are different. The antioxidant ascorbic acid (vitamin C) has the different effect on the photoinduced free radicals. In particular, in the case of black hair, the concentration of photoinduced free radicals is slightly reduced, whereas in red hair, the disappearance of the triplet in the spectrum is observed, and at the same time, the spectrum becomes a singlet, the intensity of which increases sharply. It is assumed that the antioxidants, effective for black hair, may be ineffective for red hair and vice versa. Therefore, in each, specific case is necessary to investigate the effectiveness of an antioxidant separately. © 2011 The Authors. ICS © 2011 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

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

    PubMed

    Man, Dariusz; Podolak, Marian; Engel, Grzegorz

    2006-01-01

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

  11. 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.

  12. Lipid-protein interactions in model membranes from bovine brain white matter. An ESR spin label and electron microscopy study.

    PubMed

    Hemminga, M A; Post, J F

    1976-06-04

    Lipid-protein model membranes, prepared from bovine brain white matter and containing all the lipids and Folch-Lees proteolipids, have been studied in macroscopically oriented multibilayers. To examine the lipid environment the membranes were spin labeled with the cholestane spin label (3'-spiro(2'=(N-oxyl-4',4'-dimethyl-oxazolidine))5alpha-cholestane) and a fatty acid spin label (4',4'-dimethyloxazolidine-N-oxyl derivative of 5-ketostearic acid). The ESR spectra exhibit two components arising from fairly well oriented and completely unoriented lipids. Up to a temperature of 55 degrees C the amount of oriented lipids is almost constant, being about 35%. At higher temperatures this percentage drops rapidly to zero. It is shown that the presence of unoriented lipids arises mainly from disrupted areas in the lipid bilayer structure. This is confirmed by electron miccroscopy and from an analysis of the temperature dependence of the order parameters of the spin labels. The presence of locally disrupted lipid parts in the bilayer is discussed in relation to the interaction of the brain white matter lipids with Folch-Lees protein.

  13. EXAFS study of Cu/C catalysts

    NASA Astrophysics Data System (ADS)

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

    2000-06-01

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

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

    PubMed

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

    2011-09-07

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

  15. Model membrane partition ESR study in the presence of alpha-tocopherol by a new spin probe

    SciTech Connect

    Severcan, F.; Cannistraro, S. )

    1989-08-01

    The effect of alpha-tocopherol (alpha T) on partitioning and fluidity changes occurring in phospholipid liposomes have been investigated by monitoring the X-band ESR spectrum of the high resolution amphiphilic spin probe perdeutero-di-t-butyl nitroxide (PDDTBN), which partitions in the lipid and water phase of liposomes, showing all the three resonances from each phase well resolved.

  16. Validation of ESR analyzer using Westergren ESR method.

    PubMed

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

    2007-07-01

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

  17. A study for association and interaction analysis to metabolic syndrome and the ESR1 gene on cardiovascular autonomic neuropathy in a Chinese Han population.

    PubMed

    Zeng, Fangfang; Zhou, Linuo; Tang, Zihui

    2016-01-01

    The aim of this study was to investigate the association and interaction of metabolic syndrome (MetS) and estrogen receptor alpha 1 (ESR1) gene polymorphisms on cardiovascular autonomic neuropathy (CAN). A large-scale, population-based study was conducted to analyze the interaction of MetS and ESR1 gene polymorphisms to CAN, including a total of 1977 Chinese subjects. The most common studied single nucleotide polymorphism of ESR1 gene-rs9340799, was genotyped. Multiple logistic regression (MLR) was performed to evaluate the interaction effect of environmental variables and gene polymorphisms. Interaction on an additive scale can be calculated by using the relative excess risk due to interaction (RERI), the proportion attributable to interaction (AP), and the synergy index (S). After controlling potential confounders, MLR showed that significant association between MetS and CAN (p < 0.001). Interestingly, we found that the participants with MetS bearing the minor allele G had an increased CAN prevalence comparing those with allele A (p = 0.045), and a positive interaction was estimated by using RETI = 0.396 (95 % CI 0.262 to 0.598), AP = 0.216 (95 % CI -0.784 to 1.216) and S = 1.906 (95 % CI 0.905 to 4.015). The present findings suggest that MetS is significantly associated with CAN and provide evidence for the hypothesis that MetS and ESR1 gene polymorphism (rs9340799) have interactive effects on CAN. ClinicalTrials gov Identifier NCT02461342.

  18. ESR Dating Research of Glacial Tills in Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Bi, W.; Yi, C.

    2016-12-01

    In recent years, Quaternary Glacial-chronology has been made remarkable progress in the Tibetan Platean(TP) with the development of several numeric dating techniques, such as cosmogenic nuclides(NC), optically stimulated luminescence(OSL) and 14C. In constrast, the dating of Quaternary glacial tills in 100,000 years even more than million-year has been a challenge, just because the techniques has defects themselves and the sediments were stransformed during the geological and geomorphology progress later. Electron Spin Resonance(ESR) has been becoming one of the key methods of Quaternary Glacial-chronology with wide range of dating, expecially for the sample older than 100,000 years up to million-year scale. The accurate measurement of equivalent dose significantly impacts on accuracy and reliability of ESR dating method. Therefore, the study of the mechanisms of resetting processes is fundamental for accurate and reliable ESR dating. To understand the mechanism and characteristics of quartz ESR signal resetting of different samples, a series of laboratory simulation and field observation studies were carried out, which made lots of important breakthrough. But the research in quartz ESR signal of moraines is less and the test of ESR dating method is still in the qualitative investigation. Therefor, we use ESR dating and study on the mechanism and characteristics of quartz ESR signals in tills in the Tibetan Platean. In the adjust method of Modern, the quartz ESR signals in Modern glacial tills represent residual values which can be adjusted signals in the older glacial tills. As a consequence, ESR dating of the quartz in moraines needs to be explored in deep with building models to adjust ages which are measured by ESR dating. Therefore, ESR dating will become the trusted one of the cross dating methods in Quaternary Glacial-chronology with the adjust mothod improving the accuracy of ESR dating ages.

  19. 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)

  20. ESR study of the reaction of cyclopentadienyl complexes of zirconium hydrides with benzyl halides in the presence of 2,4,6-tri-tert-butylnitrosobenzene

    SciTech Connect

    Freidlina, R.Kh.; Gasanov, R.G.; Strunkina, L.I.; Brainina, E.M.

    1986-12-20

    An ESR study was carried out on the reactions of Cp/sub 2/ArH/sub 2/ (A), Cp/sub 2/ZrH(Cl) (B), and Cp/sub 3/ArH (C) (Cp = eta/sup 5/-C/sub 5/H/sub 5/) with benzyl halides in the presence of 2,4,6-tri-tert-butylnitrosobenzene (BNB). The ESR spectrum in the case of the reaction of (C) with BNB in benzene or toluene shows ArN(O)H radicals (Ar = 2,4,6-(Me/sub 3/C)/sub 3/C/sub 6/H/sub 2/) (a/sub H/ = 11.7, a/sub H/ = 13.0, a/sub m-H/ = 1.1 Oe). The ESR spectrum under the same conditions with C/sub 6/H/sub 5/CH/sub 2/Br shows signals for (C/sub 6/H/sub 5/CH/sub 2/N(O)Ar)/sub st/ radicals (I) (C approx. 5 x 10/sup -6/ M, a/sub N/ = 13.6, a/sub ..beta..-H/ = 14.7, a/sub m-H/ = 0.8 Oe). Radicals (I) were also obtained in the reaction of (C) with C/sub 6/H/sub 5/CH/sub 2/Cl in the presence of H, but the yield was only about 10/sup -7/ M. Radicals (I) were also detected by ESR spectroscopy in the reaction of (A) or (B) with C/sub 6/H/sub 5/CH/sub 2/Br. All the reactions were carried out in an inert-gas atmosphere at about 20/sup 0/C in the absence of irradiation. The formation of radicals (I) in the reactions studied may be attributed to the radical abstraction of bromine or chlorine from the benzyl halides.

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

    PubMed Central

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

    2011-01-01

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

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

    PubMed Central

    Rogge, Matthew L.; Thune, Ronald L.

    2011-01-01

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

  3. In situ ESR/UV-vis-NIR and ATR-FTIR spectroelectrochemical studies on the p-doping of copolymers of 3-methylthiophene and 3-hexylthiophene.

    PubMed

    Cházaro-Ruiz, Luis F; Kellenberger, Andrea; Dunsch, Lothar

    2009-02-26

    A combined spectroelectrochemical study by ESR/UV-vis-NIR as well as FTIR spectroscopy on the influence of the copolymer composition on the stabilization of charges upon electrochemical p-doping is presented. As compared to the parent homopolymers 3-hexylthiophene (3-HeTh) and 3-methylthiophene (3-MeTh) which seems to be irregular, FTIR studies of the copolymer of both monomers (copMeHeTh) point to a regioregular structure. The in situ ESR and UV-vis-NIR spectroelectrochemistry at higher doping levels of the polymeric materials proves bipolarons and polaron pairs as stable charged states in poly(3-hexylthiophene) as well as the copolymer copMeHeTh. During the p-doping of poly(3-methylthiophene) bipolarons are the dominating species at higher doping levels. It is demonstrated that only the simultaneous use of both the ESR and the UV-vis-NIR spectroscopy enables the differentiation of polarons (paramagnetic) and polaron pairs (diamagnetic) in a conducting polymer.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1987-09-01

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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Regupathy, Sthanumoorthy; Nair, Madhavan Sivasankaran

    2010-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1994-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  11. Pi-dimer of an aniline dimer: an ESR-UV-vis spectroelectrochemical study.

    PubMed

    Petr, Andreas; Wei, Di; Kvarnström, Carita; Ivaska, Ari; Dunsch, Lothar

    2007-11-01

    It is shown for the first time that the most important intermediate formed during aniline polymerization, the p-aminodiphenylamine, forms a pi-dimer under oxidation at room temperature in acidified organic solvents that are used in electropolymerization. N-Phenylquinonediimine, which is generally assumed to be formed under oxidation, is only formed in basic solutions and in ionic liquids. Most of the mechanistic studies reported so far take the formation of N-phenylquinonediimine under consideration, although it is not consistent with the UV-vis spectra measured during oxidation of p-aminodiphenylamine. The formation of a pi-dimer is very well consistent with the electronic spectra of the oxidation product. In this way the pi-dimer is very important for the interpretation of the UV-vis spectra of higher oligomers and polyaniline as well. Furthermore, it offers a new interpretation of the redox behavior of p-aminodiphenylamine as found by cyclic voltammetry and has to be considered in the mechanism of the electrochemical polyaniline formation.

  12. A matrix isolation ESR and theoretical study of MgN

    NASA Astrophysics Data System (ADS)

    Hearne, Thomas S.; Yates, Sally A.; Wild, Duncan A.; McKinley, Allan J.

    2017-07-01

    Matrix isolation experiments have been conducted on the Mg14N, 25Mg14N, Mg15N, and 25Mg15N radicals which were formed by the reaction of a plume of magnesium metal produced with laser ablation and either acetonitrile vapour or nitrogen atoms. The radicals were isolated in an inert neon matrix at 4.3 K and studied with electron spin resonance spectroscopy. The ground electronic state of MgN was determined to be 4Σ-. The following magnetic parameters were determined experimentally for MgN: g⊥ = 2.004 78 (2), g∥ = 2.001 72 (4), |D| = 9797 (6) MHz, A⊥(14N) = 19.7 (2) MHz, A∥ (14N) = -4.0 (3) MHz, A⊥(15N) = 27.5 (3) MHz, A∥ (15N) = -5.7 (3) MHz, A⊥ (25Mg) = -60.7 (5) MHz, and A∥(25Mg) = -65 (3) MHz. The low-lying electronic states of MgN were also investigated using the complete active space multiconfigurational self-consistent field technique. By plotting the potential energy surface, theoretical parameters for the ground state with a configuration of 5σ26σ27σ12π12π1 were able to be determined, including re = 2.090 Å and De = 11.28 kcal/mol.

  13. 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

  14. The reaction mechanism of p-toluenediamine anodic oxidation: an in situ ESR-UV/Vis/NIR spectroelectrochemical study.

    PubMed

    Goux, Aurélie; Pratt, Dominic; Dunsch, Lothar

    2007-10-08

    In situ ESR-UV/Vis spectroelectrochemistry is applied to obtain new insights into the intermediates and reaction products of the anodic oxidation of p-toluenediamine in aqueous solution at different pH values. A strong pH dependence of the stability of the cation radical is found. While the absence of a stable radical was proved by ESR spectroscopy at pH 2 and 10, this radical is detected at medium pH values and assigned to the semiquinonediimine structure. The UV/Vis absorption of the radical is observed at these pH values as well. The p-toluenediimine intermediate and the trimeric reaction product were followed during the electrode reaction by UV/Vis spectroscopy at all pH values.

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

    NASA Astrophysics Data System (ADS)

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

    1997-06-01

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

  16. 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.

  17. 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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. 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.

  19. [Identification of irradiated abalone by ESR spectroscopy].

    PubMed

    Song, Yeping; Wang, Chuanxian; Yang, Zhenyu; Zhong, Weike; Geng, Jinpei; Lu, Di; Ding, Zhuoping

    2012-05-01

    To establish an analytical method for the detection and identification of irradiated abalone by electron spin resonance spectroscopy. Electron spin resonance (ESR) was used to study the spectral characteristics of abalone and the characteristic peak for quantitation. There were obvious different ESR spectra between unirradiated and irradiated abalone. The g factor for unirradiated abalone was 2.0055-2.0060, the g1 and g2 factor for irradiated abalone were (2.0027 +/- 0.0001) and (1.9994 +/- 0.0001), respectively. The ESR signal intensity of characteristic peak was positively correlated with absorbed dose in the range of 0.5 - 10 kGy, left peak was the characteristic peak for quantitation and the detection limit was < or = 0.5 kGy. It was difficult to quantitate when the absorbed dose was over 10 kGy. ESR characteristic peak and g factor were able to qualitatively determine the irradiation of abalone. ESR spectroscopy is an effective method to determine whether the abalone being irradiated or not.

  20. 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. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2008-12-01

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

  2. Dynamics and Ordering of Lipid Spin-Labels along the Coexistence Curve of Two Membrane Phases: An ESR Study

    PubMed Central

    Smith, Andrew K; Freed, Jack H.

    2012-01-01

    An analysis of electron spin resonance (ESR) spectra from compositions along the liquid-ordered (Lo) and liquid-disordered (Ld) coexistence curve from the brain-sphingomyelin/dioleoylphosphatidylcholine/cholesterol (SPM/DOPC/Chol) model lipid system was performed to characterize the dynamic structure on a molecular level of these coexisting phases. We obtained 200 continuous-wave ESR spectra from glycerophospholipid spin-labels labeled at the 5, 7, 10, 12, 14, and 16 carbon positions of the 2nd acyl chain, a sphingomyelin spin-label labeled at the 14 carbon position of the amide-linked acyl chain, a headgroup-labeled glycerophospholipid, a headgroup-labeled sphingomyelin, and the cholesterol analogue spin-label cholestane all within multi-lamellar vesicle suspensions at room temperature. The spectra were analyzed using the MOMD (microscopic-order macroscopic-disorder) model to provide the rotational diffusion rates and order parameters which characterize the local molecular dynamics in these phases. The analysis also incorporated the known critical point and invariant points of the neighboring three-phase triangle along the coexistence curve. The variation in the molecular dynamic structures of coexisting Lo and Ld compositions as one moves toward the critical point is discussed. Based on these results, a molecular model of the Lo phase is proposed incorporating the “condensing effect” of cholesterol on the phospholipid acyl chain dynamics and ordering and the “umbrella model” of the phospholipid headgroup dynamics and ordering. PMID:22586732

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

    NASA Astrophysics Data System (ADS)

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

    1997-10-01

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

  4. In situ spectroelectrochemistry of poly(N,N'-ethylenebis(salicylideneiminato)Cu(II)).

    PubMed

    Tarábek, Ján; Rapta, Peter; Kalbác, Martin; Dunsch, Lothar

    2004-10-01

    In situ ESR, UV-visible, and FT-IR-ATR spectroelectrochemistry were used to study the charge transfer for electrochemically synthesized poly(N,N'-ethylenebis(salicylideneiminato)Cu(II)), which represents a macromolecular metal chelate with ESR-active central metal ions. Structural evidence for different charged states in electroactive poly(Cu(II)-salen) was obtained from ESR, UV-visible, and FT-IR spectra under reversible redox cycling. The changes in a characteristic broad ESR line without hyperfine splitting originating from Cu(II) as well as in the corresponding UV-visible and infrared spectra are discussed in order to describe an electron transfer to the redox-active sites within the polymer chains in detail.

  5. 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.

  6. Molecular cloning of ESR2 and gene expression analysis of ESR1 and ESR2 in the pituitary gland of the Chinese alligator (Alligator sinensis) during female reproductive cycle.

    PubMed

    Zhang, Ruidong; Yin, Yanan; Sun, Long; Yan, Peng; Zhou, Yongkang; Wu, Rong; Wu, Xiaobing

    2017-08-05

    Estrogens play critical roles in reproductive physiology via estrogen receptors (ESRs) in vertebrates, including reptiles. Chinese alligator (Alligator sinensis) is an endemic and endangered reptile species in China. In the present study, we cloned ESR2 gene from the ovary using rapid amplification of cDNA ends (RACE), investigated the spatial expression of ESRs in various tissues and temporal expression of ESRs in the pituitary glands during the reproductive cycle in Chinese alligators by quantitative real-time PCR (qPCR). Bioinformatics and phylogenetic analysis of deduced ESR2 protein were also performed. The full-length cDNA of the ESR2 is 1647bp in length, with an open-reading frame encoding 548 amino acids. The bioinformatics analysis indicated that the deduced amino acid sequence of alligator ESR2 was highly conserved with that of other vertebrate species. In addition, compared to human ESR2, the 14 amino acids in the alligator ESR2 that are essential for specific recognition of estradiol are entirely conserved. The phylogenetic analysis showed that alligators were more closely related to birds than to other reptiles. The results of qPCR showed that the tissue distribution patterns of both ESR subtype mRNAs appeared to be different. In male tissues, the highest mRNA level of both ESRs is in the liver. While in female tissues, ESR1 and ESR2 showed the highest mRNA level in the hypothalamus and pituitary gland, respectively. During the female reproductive cycle, the expression level of ESR1 mRNA increased from the initial post-hibernation period to the reproductive period, reached its peak in the reproductive period, and then decreased in the autumn active period and hibernation period. Conversely, the highest transcription level of ESR2 was observed in the hibernation period. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Mn doping effect on optical and ESR studies of Zn{sub 1-x}Mn{sub x}O compound sintered at different temperatures

    SciTech Connect

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

    2016-05-06

    Polycrystalline bulk samples of Zn{sub 1-x}Mn{sub x}O 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.

  8. Conformational Distributions and Hydrogen Bonding in Gel and Frozen Lipid Bilayers: A High Frequency Spin-Label ESR Study

    PubMed Central

    Dzikovski, Boris; Tipikin, Dmitriy

    2012-01-01

    The ESR parameters of PC spin labels in frozen membranes do not simply represent the membrane polarity or water penetration profile. Instead, they show a distribution between hydrogen-bonded (HB) and non-hydrogen bonded (non-HB) states, which is affected by a number of factors in the membrane composition. Similar to the exclusion of solutes from crystallizing solvents, the pure bulk gel phase excludes nitroxides, forcing acyl chains to take bent conformations. In these conformations the nitroxide is hydrogen-bonded. Furthermore, upon gradual cooling in the supercooled gel PC labels undergo slow lateral aggregation resulting in a broad background signal. However, if the sample is instantly frozen, this background is replaced by the HB component. In membranes with cholesterol the observed HB/ non-HB ratio can best be described by a partition-like equilibrium between nitroxides located in defects of lipid structure within the hydrophobic core and those close to the membrane surface. PMID:22324811

  9. 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.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1993-03-01

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

  12. Dynamics of CO2- radiation defects in natural calcite studied by ESR, electron spin echo and electron spin relaxation

    NASA Astrophysics Data System (ADS)

    Wencka, M.; Lijewski, S.; Hoffmann, S. K.

    2008-06-01

    ESR spectra were recorded in the X-band (9.6 GHz) and in the W-band (94 GHz) and electron spin relaxation was measured by electron spin echo (ESE) in the temperature range 4.2-300 K for radicals in natural calcite samples obtained from a cave stalactite and a dripstone layer. Four types of carbonate radical spectra and two sulfate radical spectra were identified and high accuracy g-factors were derived. Time and temperature behaviour of the spectra show that the dominating CO2- radicals are rigidly bonded or undergo free reorientations, whereas CO3-, SO2- and SO3- only undergo free reorientations. Below 200 K the free reorientations of CO2- are suppressed and a hindered rotation around single local axis appears. The ESE detected spectrum proves that the lines of free rotating radicals are homogeneously broadened, thus they cannot participate in electron spin echo formation. Spin-lattice relaxation data show that CO2- radicals are decoupled from lattice phonons and relax via local mode tunnelling motion between inequivalent oxygen positions of CO2- molecules. The tunnelling appears in two excited vibrational states of energy 71 and 138 cm-1. Librational motions of CO2- molecules were detected by electron spin echo decay (phase relaxation) with energy 153 cm-1. Two kinds of impurity hydrogen atoms were distinguished from ESEEM: in-water inclusions and water coordinated to the calcium ions.

  13. ESR (Erythrocyte Sedimentation Rate) Test

    MedlinePlus

    ... AACC products and services. Advertising & Sponsorship: Policy | Opportunities Erythrocyte Sedimentation Rate (ESR) Share this page: Was this ... with conditions that inhibit the normal sedimentation of red blood cells, such as a high red blood cell count ( ...

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

    NASA Astrophysics Data System (ADS)

    Duan, Yuhua; Zhang, Kaiming; Xie, Xide

    1994-12-01

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

  15. Isotope effects in ESR spectroscopy.

    PubMed

    Stößer, Reinhard; Herrmann, Werner

    2013-06-07

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

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

    PubMed

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

    2009-05-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

  18. 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.

  19. 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

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

    PubMed

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

    2010-01-01

    The catalytic decomposition of hydrogen peroxide by Cu(II) complexes with polymers bearing L-alanine (PAla) and glycylglycine (PGlygly) in their side chain was studied in alkaline aqueous media. The reactions were of pseudo-first order with respect to [H(2)O(2)] and [L-Cu(II)] (L stands for PAla or PGlygly) and the reaction rate was increased with pH increase. The energies of activation for the reactions were determined at pH 8.8, in a temperature range of 293-308 K. A suitable mechanism is proposed to account for the kinetic data, which involves the Cu(II)/Cu(I) redox pair, as has been demonstrated by ESR spectroscopy. The trend in catalytic efficiency is in the order PGlygly>PAla, due to differences in modes of complexation and in the conformation of the macromolecular ligands.

  1. 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).

  2. Spectroscopic, thermal, catalytic and biological studies of Cu(II) azo dye complexes

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Shoair, A. F.; Hussein, M. A.; El-Boz, R. A.

    2017-08-01

    New complexes of copper(II) with azo compounds of 5-amino-2-(aryl diazenyl)phenol (HLn) are prepared and investigated by elemental analyses, molar conductance, IR, 1H NMR, UV-Visible, mass, ESR spectra, magnetic susceptibility measurements and thermal analyses. The complexes have a square planar structure and general formula [Cu(Ln)(OAc)]H2O. Study the catalytic activities of Cu(II) complexes toward oxidation of benzyl alcohol derivatives to carbonyl compounds were tested using H2O2 as the oxidant. The intrinsic binding constants (Kb) of the ligands (HLn) and Cu(II) complexes (1-4) with CT-DNA are determined. The formed compounds have been tested for biological activity of antioxidants, antibacterial against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and yeast Candida albicans. Antibiotic (Ampicillin) and antifungal against (Colitrimazole) and cytotoxic compounds HL1, HL2, HL3 and complex (1) showed moderate to good activity against S. aureus, E. coli and Candida albicans, and also to be moderate on antioxidants and toxic substances. Molecular docking is used to predict the binding between the ligands with the receptor of breast cancer (2a91).

  3. Development of Prototype Production ESR Facilities

    DTIC Science & Technology

    1977-07-01

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

  4. Physics book: CRYRING@ESR

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Özsayin, Fulya; Polat, Mustafa

    2011-06-01

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

  6. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  8. Anisotropic magnetic interactions and spin dynamics in the spin-chain compound Cu (py) 2Br2 : An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Zeisner, J.; Brockmann, M.; Zimmermann, S.; Weiße, A.; Thede, M.; Ressouche, E.; Povarov, K. Yu.; Zheludev, A.; Klümper, A.; Büchner, B.; Kataev, V.; Göhmann, F.

    2017-07-01

    We compare theoretical results for electron spin resonance (ESR) properties of the Heisenberg-Ising Hamiltonian with ESR experiments on the quasi-one-dimensional magnet Cu (py) 2Br2 (CPB). Our measurements were performed over a wide frequency and temperature range giving insight into the spin dynamics, spin structure, and magnetic anisotropy of this compound. By analyzing the angular dependence of ESR parameters (resonance shift and linewidth) at room temperature, we show that the two weakly coupled inequivalent spin-chain types inside the compound are well described by Heisenberg-Ising chains with their magnetic anisotropy axes perpendicular to the chain direction and almost perpendicular to each other. We further determine the full g tensor from these data. In addition, the angular dependence of the linewidth at high temperatures gives us access to the exponent of the algebraic decay of a dynamical correlation function of the isotropic Heisenberg chain. From the temperature dependence of static susceptibilities, we extract the strength of the exchange coupling (J /kB=52.0 K ) and the anisotropy parameter (δ ≈-0.02 ) of the model Hamiltonian. An independent compatible value of δ is obtained by comparing the exact prediction for the resonance shift at low temperatures with high-frequency ESR data recorded at 4 K . The spin structure in the ordered state implied by the two (almost) perpendicular anisotropy axes is in accordance with the propagation vector determined from neutron scattering experiments. In addition to undoped samples, we study the impact of partial substitution of Br by Cl ions on spin dynamics. From the dependence of the ESR linewidth on the doping level, we infer an effective decoupling of the anisotropic component J δ from the isotropic exchange J in these systems.

  9. ESR Study of Electron-Nuclear Dipolar Relaxation for AsO 44-Spin Probe in the Paraelectric Phase of KH 2AsO 4

    NASA Astrophysics Data System (ADS)

    Rakvin, B.; Merunka, D.

    1997-05-01

    Saturation behavior of allowed and forbidden ESR transition of AsO44-paramagnetic probe in KH2AsO4was studied in the wide temperature interval around the paraelectric-ferroelectric phase transition,Tc. The ratios between forbidden and allowed line intensities were employed to deduce information on the electron-nuclear dipolar (END) relaxation mechanism. It was shown that a proton END relaxation mechanism exhibits an extremal temperature behavior in the paraelectric phase around 230 K. The extremal temperature behavior was described by employing a model of proton hopping along the O-H···O bonds around the paramagnetic centers, and the correlation time of this hopping was estimated in the wide temperature range in the paraelectric phase (150-330 K). The temperature dependence of effective proton distance from the neighbor oxygens was obtained, and it was discussed in terms of a localization of the spin density on these oxygens caused by charge inbalance in the As-O bonds in the ferroelectric phase.

  10. In situ ESR-UV-Vis-NIR spectroelectrochemical study of the p-doping of poly[2-(3-thienyl)ethyl acetate] and its hydrolyzed derivatives.

    PubMed

    Cházaro-Ruiz, Luis F; Kellenberger, Andrea; Jähne, Evelin; Adler, Hans-Jürgen; Khandelwal, Taruna; Dunsch, Lothar

    2009-08-14

    The electrochemical oxidation of the chemically prepared polymer poly[2-(3-thienyl)ethyl acetate] (PTEtAc), its partially hydrolyzed derivative PTEtAcOH and the fully hydrolyzed compound poly[2-(3-thienyl)ethanol] (PTEtOH) was studied by in situ electron spin resonance (ESR)/UV-Vis-NIR spectroelectrochemistry. The spectroelectrochemical response of these films on ITO substrates was analyzed with respect to the influence of the functionalized alkyl side chain on polymer doping. The simultaneous use of both electron spin resonance and UV-Vis-NIR spectroscopy allows the analysis of the nature, extent and stability of the charge carriers electrogenerated during p-doping. It was found that PTEtAc has a higher capacity for charged species due to the flexibility of the longer side chains making the redox states more stable at different doping levels. At low doping levels the charged states are dominated by polaronic species while at high doping levels bipolarons and diamagnetic polaron pairs are formed. The presence of the OH groups in the polymer side chains of the hydrolyzed derivatives favors hydrogen bonds. These interactions by hydrogen bonding fix the conjugated chains thus making a charge-discharge reaction more difficult. At high doping levels the hydrolyzed polymers favor the formation of polaron pairs.

  11. High field ESR study of the pi-d interaction effect in beta-(BDA-TTP)2MCl4 (M=Fe, Ga)

    NASA Astrophysics Data System (ADS)

    Tokumoto, Takahisa; Vantol, J.; Brunel, L.-C.; Choi, E. S.; Brooks, J. S.; Kaihatsu, T.; Akutsu, H.; Yamada, J.

    2007-03-01

    Novel magnetic organic conductors with pi-d interaction have commanded attention since the discovery of field induced superconductivity. One of them, beta-(BDA-TTP)2FeCl4, has alternating donor molecules and quasi 2D electrical properties. Previous studies of electrical and magnetic properties show an M-I transition at 120K and an AF transition at TN=8.5K, suggesting an exchange interaction between the conduction electrons and the Fe^3+ d-electrons. The properties of beta-(BDA-TTP)2GaCl4 are similar with exception of the absence of the AF transition, which is apparently due to the absence of pi-d exchange interaction. We report angular/temperature dependent 240GHz quasi optical ESR measurements on both compounds to probe the magnetic properties. The Ga compound signals follow the donor molecule structure, and show no magnetic order at any temperature. The Fe compound signals are quite different from the Ga compound, and exhibit AF behavior below TN. The difference of Fe and Ga compounds will be discussed in terms of the interaction between localized and itinerant magnetic moments.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2004-05-01

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

  14. 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

  15. Alloying effect via comparative studies of ethanol dehydrogenation on Cu(1 1 1), Cu3Pd(1 1 1), and Cu3Pt(1 1 1)

    NASA Astrophysics Data System (ADS)

    Wu, Ruitao; Wang, Lichang

    2017-06-01

    Ethanol dehydrogenations on Cu(1 1 1), Cu3Pd(1 1 1), and Cu3Pt(1 1 1) were studied using density functional theory with a PBE functional. The α-C-H and β-C-H scissions are endothermic on all surfaces while the O-H scission is exothermic on Cu(1 1 1) and Cu3Pt(1 1 1) but endothermic on Cu3Pd(1 1 1). The ethanol dehydrogenation occurs on Cu(1 1 1) through both α-C-H and O-H scissions but on Cu3Pd(1 1 1) and Cu3Pt(1 1 1) through only α-C-H scission. Furthermore, alloying Pt or Pd with Cu shows an increase in reaction rate at 493 K by more than 3 orders of magnitude, thus illustrating the promise of alloying Pt or Pd in Cu catalysts for ethanol dehydrogenation.

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

    PubMed

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

    2014-08-01

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

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

    PubMed

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

    2009-12-01

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

  18. 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.

  19. 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.

  20. 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.

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

    PubMed

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

    2013-02-01

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

  2. ESR spectra of oxygen radical-ions in kaolinite

    SciTech Connect

    Kharlamov, G.V.; Ivan`kin, I.A.; Gal`tsova, E.A. |

    1992-07-01

    The oxygen adsorbed on the surface of oxide systems may be stabilized as O{sub 2}{sup {minus}} radical-ions. This form of stabilization has been studied extensively by ESR spectroscopy for various catalytic systems. These radical-ions may also be stabilized in the structure of crystals as point defects. The existence of paramagnetic sites in kaolinite has long been known. Various workers have studied ESR spectra in kaolinites. However, no uniform opinion has emerged concerning the nature of the paramagnetic sites. Mank has carried out a detailed study of ESR spectra in kaolinites. The observed ESR signals were assigned to the paramagnetic form of oxygen O{sup {minus}}, stabilized on Al{sup 3+} and the hydroxyl radical. The possibility of other paramagnetic oxygen forms distributed in defects of the mineral structure was also noted. In light of the importance of the study of defects in the structure of silicate systems, the authors investigated the ESR signals of natural kaolinites in order to elucidate the fine details of these spectra and elucidate the nature of the point defects. 7 refs., 2 figs.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1992-11-01

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

  5. 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.

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

    SciTech Connect

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

    2016-05-23

    The Electron spin resonance studies on the reduction process of nitroxyl spin probes were carried out for 1mM {sup 14}N- 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 {sup 14}N- 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.

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

    PubMed

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

    2002-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Yang, Zhongyu; Becker, James; Saxena, Sunil

    2007-10-01

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

  9. Comparison of the DAS28-CRP and DAS28-ESR in patients with rheumatoid arthritis.

    PubMed

    Sengul, Ilker; Akcay-Yalbuzdag, Seniz; Ince, Bugra; Goksel-Karatepe, Altinay; Kaya, Taciser

    2015-07-01

    To compare the Disease Activity Score with 28 joint (DAS28) using erythrocyte sedimentation rate (ESR) (DAS28-ESR) and DAS28 using C-reactive protein (CRP) (DAS28-CRP) with thresholds validated for DAS28-ESR in Turkish patients with rheumatoid arthritis. The DAS28 data of 112 patients with rheumatoid arthritis followed in a local outpatient clinic were used. First, the correlation between DAS28-CRP and DAS28-ESR and the correlation between their unique components ([0.36 × In (CRP + 1) + 0.96] and [0.70 × In (ESR)]) were analyzed. Second, a Bland-Altman plot was constructed for the evaluation of the level of agreement between DAS28-CRP and DAS28-ESR. Lastly, the agreement between these two methods was analyzed by κ coefficient. Although there was a strong correlation between DAS28-CRP and DAS28-ESR, the correlation between their unique components was fair. Although more than 95% of the point data fall between the upper and lower bounds of the limit of agreement, the percentage error (46%) was higher than the acceptable proportion of 30%. The κ coefficient of agreement between DAS28- ESR and DAS28-CRP with validated thresholds for DAS28-ESR was 0.42, which was close to the lower boundary for moderate agreement. The results of this study demonstrated that there is discordance between DAS28-ESR and DAS28-CRP with the validated thresholds for DAS28-ESR. Using the DAS28-CRP with threshold values validated for DAS28-ESR may lead to errors in the determination of disease activity and therefore may lead to errors in the management of patients with rheumatoid arthritis. © 2015 Asia Pacific League of Associations for Rheumatology and Wiley Publishing Asia Pty Ltd.

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

    PubMed Central

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

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Bjerre, Nis

    1982-03-01

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

  12. ESR

    MedlinePlus

    ... infections Infection of the heart or heart valves Rheumatic fever Severe skin infections, such as erysipelas Tuberculosis Lower- ... rate References Pisetsky DS. Laboratory ... arthritis Sickle cell anemia Systemic lupus erythematosus Temporal arteritis ...

  13. A Review of Estrogen Receptor α Gene (ESR1) Polymorphisms, Mood, and Cognition

    PubMed Central

    Sundermann, Erin E.; Maki, Pauline M.; Bishop, Jeffrey R.

    2010-01-01

    OBJECTIVE There are significant individual differences in the extent to which mood and cognition change as a function of reproductive stage, menstrual phase, postpartum, and hormone therapy. This review explores the extent to which variations or polymorphisms in the estrogen receptor α gene (ESR1) predict cognitive and mood outcomes. METHODS A literature search was conducted from 1995 to November 2009 through PubMed, EMBASE, and PsychINFO. Twenty-five manuscripts were reviewed that summarize investigations of ESR1 in mental health. RESULTS Among studies investigating ESR1 in relation to cognition, 11 of 14 case-control studies reported an association between ESR1 polymorphisms and risk for developing dementia. Three of four prospective cohort studies reported an association between ESR1 polymorphisms and significant cognitive decline. There are inconsistencies between case-control and cohort studies regarding whether specific ESR1 alleles increase or decrease the risk for cognitive dysfunction. The relationships between ESR1 and cognitive impairment tend to be specific to or driven by women and restricted to risk for Alzheimer’s disease rather than other dementia causes. Three of five studies examining ESR1 polymorphisms in relation to anxiety or depressive symptoms found significant associations. Significant associations have also been reported between ESR1 polymorphisms and childhood-onset mood disorder and premenstrual dysphoric disorder. CONCLUSIONS A strong relationship between ESR1 variants and cognitive outcomes is evident and preliminary evidence suggests a role of the ESR1 gene in certain mood outcomes. Insights into the discordant results will come from future studies that include haplotype analyses, analyses within specific ethnic/racial populations, and gender-stratified analyses. PMID:20616674

  14. Intronic SNP in ESR1 encoding human estrogen receptor alpha is associated with brain ESR1 mRNA isoform expression and behavioral traits.

    PubMed

    Pinsonneault, Julia K; Frater, John T; Kompa, Benjamin; Mascarenhas, Roshan; Wang, Danxin; Sadee, Wolfgang

    2017-01-01

    Genetic variants of ESR1 have been implicated in multiple diseases, including behavioral disorders, but causative variants remain uncertain. We have searched for regulatory variants affecting ESR1 expression in human brain, measuring allelic ESR1 mRNA expression in human brain tissues with marker SNPs in exon4 representing ESR1-008 (or ESRα-36), and in the 3'UTR of ESR1-203, two main ESR1 isoforms in brain. In prefrontal cortex from subjects with bipolar disorder, schizophrenia, and controls (n = 35 each; Stanley Foundation brain bank), allelic ESR1 mRNA ratios deviated from unity up to tenfold at the exon4 marker SNP, with large allelic ratios observed primarily in bipolar and schizophrenic subjects. SNP scanning and targeted sequencing identified rs2144025, associated with large allelic mRNA ratios (p = 1.6E10-6). Moreover, rs2144025 was significantly associated with ESR1 mRNA levels in the Brain eQTL Almanac and in brain regions in the Genotype-Tissue Expression project. In four GWAS cohorts, rs2104425 was significantly associated with behavioral traits, including: hypomanic episodes in female bipolar disorder subjects (GAIN bipolar disorder study; p = 0.0004), comorbid psychological symptoms in both males and females with attention deficit hyperactivity disorder (GAIN ADHD, p = 0.00002), psychological diagnoses in female children (eMERGE study of childhood health, subject age ≥9, p = 0.0009), and traits in schizophrenia (e.g., grandiose delusions, GAIN schizophrenia, p = 0.0004). The first common ESR1 variant (MAF 12-33% across races) linked to regulatory functions, rs2144025 appears conditionally to affect ESR1 mRNA expression in the brain and modulate traits in behavioral disorders.

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

    NASA Astrophysics Data System (ADS)

    Olenga, Antoine

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

  16. 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.

  17. ESR1 mutations: Moving towards guiding treatment decision-making in metastatic breast cancer patients.

    PubMed

    Angus, Lindsay; Beije, Nick; Jager, Agnes; Martens, John W M; Sleijfer, Stefan

    2017-01-01

    Mutations in the gene coding for the estrogen receptor (ER), ESR1, have been associated with acquired endocrine resistance in patients with ER-positive metastatic breast cancer (MBC). Functional studies revealed that these ESR1 mutations lead to constitutive activity of the ER, meaning that the receptor is active in absence of its ligand estrogen, conferring resistance against several endocrine agents. While recent clinical studies reported that the occurrence of ESR1 mutations is rare in primary breast cancer tumors, these mutations are more frequently observed in metastatic tissue and circulating cell-free DNA of MBC patients pretreated with endocrine therapy. Given the assumed impact that the presence of ESR1 mutations has on outcome to endocrine therapy, assessing ESR1 mutations in MBC patients is likely to be of significant interest to further individualize treatment for MBC patients. Here, ESR1 mutation detection methods and the most relevant pre-clinical and clinical studies on ESR1 mutations regarding endocrine resistance are reviewed, with particular interest in the ultimate goal of guiding treatment decision-making based on ESR1 mutations. Copyright © 2016 The Author(s). Published by Elsevier Ltd.. All rights reserved.

  18. Nuclear reactions in the storage ring ESR with EXL

    NASA Astrophysics Data System (ADS)

    Kröll, Th; von Schmid, M.; Zamora, J. C.; Bagchi, S.; Bönig, S.; Csatlós, M.; Dillmann, I.; Dimopoulou, C.; Egelhof, P.; Eremin, V.; Furuno, T.; Geissel, H.; Gernhäuser, R.; Harakeh, M. N.; Hartig, A. L.; Ilieva, S.; Kalantar-Nayestanaki, N.; Kiselev, O.; Kollmus, H.; Kozhuharov, C.; Krasznahorkay, A.; Kuilman, M.; Litvinov, S.; Litvinov, Yu A.; Mahjour-Shafiei, M.; Mutterer, M.; Nagae, D.; Najafi, M. A.; Nociforo, C.; Nolden, F.; Popp, U.; Rigollet, C.; Roy, S.; Scheidenberger, C.; Steck, M.; Streicher, B.; Stuhl, L.; Thürauf, M.; Uesaka, T.; Weick, H.; Winfield, J. S.; Winters, D.; Woods, P. J.; Yamaguchi, T.; Yue, K.; Zenihiro, J.; EXL Collaboration

    2016-06-01

    The EXL project aims to study nuclear structure by direct reactions in inverse kinematics at the storage rings of the future FAIR facility. In this contribution, we present the status of the project: the technical implementation at the ESR at GSI and preliminary results of the EXL campaign in 2012, the first using also a radioactive beam.

  19. Conventional machining of ESR 4340 steel

    NASA Astrophysics Data System (ADS)

    Niji, K. K.

    1980-07-01

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

  20. ESR and iron status in pregnancy.

    PubMed

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

    1997-10-01

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

  1. 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.

  2. UV-visible, Raman and E.S.R. studies of gamma-irradiated NiO-doped sodium metaphosphate glasses.

    PubMed

    ElBatal, Fatma H; Morsi, Reham M; Ouis, Mona A; Marzouk, Samir Y

    2010-11-01

    UV-visible spectroscopic measurements of Ni-doped sodium phosphate glasses were carried out before and after successive gamma irradiation. The undoped glass reveals strong UV absorption originating from trace iron impurities. NiO-doped glasses show characteristic absorption bands due mainly to octahedral coordination of Ni(2+) ions. Gamma irradiation produces induced bands generated from intrinsic defects and extrinsic defects. The changes in the spectroscopic data are discussed in relation to the structural evolution caused by the changes in composition and coordination state of nickel ions. The change in the growth behaviour of the induced bands is related to the annihilation or approach saturation of these characteristic induced bands. Raman and E.S.R. spectroscopic measurements confirm the presence of nickel as Ni(2+) ions in octahedral state. Copyright © 2010 Elsevier B.V. All rights reserved.

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

    PubMed

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

    1985-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Singh, Vinod P.; Singh, Pooja

    2013-03-01

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

  5. ESR1 and its antagonist fulvestrant in pituitary adenomas.

    PubMed

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

    2017-03-05

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

  6. Synthesis, characterization, and theoretical studies of Co(II) and Cu(II) complexes of 1-[(5-mercapto-[1,3,4]thiadiazol-2-ylimino)-methyl]-naphthalen-2-ol and its interaction with Cu nanoparticles

    NASA Astrophysics Data System (ADS)

    El-Wakiel, Nadia; El-Sayed, Yusif; Gaber, Mohamed

    2011-08-01

    The electronic absorption spectra of Schiff base namely 1-[(5-mercapto-[1,3,4]thiadiazol-2-ylimino)-methyl]-naphthalen-2-ol (H 2L) was studied in organic solvents of different polarity as well as in universal buffer solutions of varying pH values at room temperature; the pK a values were calculated. The effect of Co(II) and Cu(II) ions on the electronic absorption spectra of H 2L was also assigned and the stability constants of the complexes were calculated. The stoichiometry of the metal complexes was determined spectrophotometrically. Solid Co(II) and Cu(II) complexes with H 2L have been synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic as well as ESR spectral studies. The thermal decomposition of the metal complexes was studied by TGA and DTA techniques. The thermo-kinetic parameters; activation energy, pre-exponential factor and entropy of activation were estimated. The interaction between the Schiff base under investigation and the copper nanoparticles in the ground and excited state was considered. The fluorescence quenching rate constant of Schiff base by Cu nanoparticles has a large value.

  7. 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.

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

    SciTech Connect

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

    2009-09-15

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

  9. Surface characterization of Cu-Ti systems: an IR study

    NASA Astrophysics Data System (ADS)

    Boccuzzi, F.; Baricco, M.; Guglielminotti, E.

    1993-06-01

    A comparative study of the surface properties of Cu-Ti samples prepared by impregnation of TiO 2 with a Cu(NO 3) 2 solution or from amorphous CuTi alloy precursors diluted with TiO 2 has been made. The samples were submitted to vacuum and H 2 treatments at increasing temperatures, from 493 up to 773 K; at the end of the pretreatments the specimens were contacted with CO, from RT up to 573 K. The surface species produced were monitored by FTIR spectroscopy. On all the samples a band of CO adsorbed on Cu surface sites, significantly blue-shifted in comparison with that observed on Cu monocrystalline surfaces and on Cu particles supported on other n-type oxidic semiconductors, was observed. The blue-shift, that is maximum on the most strongly reduced samples, was interpreted as due to an electronic interaction of copper with reduced titania and to the fact that, on the more strongly reduced samples, copper particles are almost completely covered by reduced titania and copper sites are almost isolated. The NO interaction on CO precovered samples produces a strong intensity and a red-shift of the CO absorption band, indicating that in oxidizing conditions and in the presence of CO the exposed Cu grows up.

  10. Targeting ESR1-Mutant Breast Cancer

    DTIC Science & Technology

    2015-09-01

    AWARD NUMBER: W81XWH-14-1-0359 TITLE: Targeting ESR1-Mutant Breast Cancer PRINCIPAL INVESTIGATOR: Dr. Sarat Chandarlapaty CONTRACTING...31 Aug 2015 4. TITLE AND SUBTITLE Targeting ESR1-Mutant Breast Cancer 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-14-1-0359 5c. PROGRAM ELEMENT...mutations found in breast cancer using both structural and cell based assays. We have now have evidence for the effects of the most recurrent

  11. Targeting ESR1-Mutant Breast Cancer

    DTIC Science & Technology

    2015-09-01

    AWARD NUMBER: W81XWH-14-1-0359 TITLE: Targeting ESR1-Mutant Breast Cancer PRINCIPAL INVESTIGATOR: Dr. Sarat Chandarlapaty CONTRACTING...ORGANIZATION: Sloan Kettering Institute for Cancer Research New York, NY 10065 REPORT DATE: September 2015 TYPE OF REPORT: Annual Technical Report...31 Aug 2015 4. TITLE AND SUBTITLE Targeting ESR1-Mutant Breast Cancer 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-14-1-0359 5c. PROGRAM ELEMENT

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

    SciTech Connect

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

    1991-01-01

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

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

    PubMed

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Tuner, H.

    2013-01-01

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

  15. 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.

  16. 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.

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

    PubMed

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

    2015-11-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

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

    PubMed

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

    2009-04-01

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

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  2. Effects of Ce{sup 4+}/sulfato complex formation in the Belousov-Zhabotinskii reaction: ESR studies of malonyl radical formation

    SciTech Connect

    Foersterling, H.D.; Stuk, L.

    1992-04-02

    The authors investigated the effects of the formation of sulfato complexes from Ce{sup 4+} and H{sub 2}SO{sub 4} on the oxidation of malonic acid (MA) by Ce{sup 4+} in the Belousov-Zhabotinskii (BZ) reaction. The authors found from measuring malonyl radical concentrations in an ESR flow experiment that the rate of formation of sulfato complexes is very fast compared to the rate of the MA/Ce{sup 4+} reaction. This result is important in the theory of the BZ reaction; there is no difference in the reaction rate whether Ce{sup 4+} is freshly produced in the autocatalytic cycle or it is introduced in the sulfato-complexed form. Moreover, the authors did absolute calibrations of the malonyl radical concentrations by using Mn{sup 2+} and 3-carbamoyl-PROXYL as calibration standards. From these concentrations the authors calculated malonyl radical self-decay rates of 4.2 x 10{sup 8} M{sup -1}s{sup -1} in 1 M H{sub 2}SO{sub 4} and 1.5 x 10{sup 9} M{sup -1} s{sup -1} in 2 M HClO{sub 4-}. 23 refs., 6 figs., 5 tabs.

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

    PubMed

    Joshi, A; Moss, H; Riesz, P

    1978-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  5. 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

  6. Electronic structures of Cu2O,Cu4O3 , and CuO: A joint experimental and theoretical study

    DOE PAGES

    Wang, Y.; Lany, S.; Ghanbaja, J.; ...

    2016-12-14

    We present a joint experimental and theoretical study for the electronic structures of copper oxides including Cu2O, CuO, and the metastable mixed-valence oxide Cu4O3. The optical band gap is determined by experimental optical absorption coefficient, and the electronic structure in valence and conduction bands is probed by photoemission and electron energy loss spectroscopies, respectively. Furthermore, we compare our experimental results with many-body GW calculations utilizing an additional on-site potential for d-orbital energies that facilitates tractable and predictive computations. The side-by-side comparison between the three oxides, including a band insulator (Cu2O) and two Mott/charge-transfer insulators (CuO, Cu4O3) leads to a consistentmore » picture for the optical and band-structure properties of the Cu oxides, strongly supporting indirect band gaps of about 1.2 and 0.8 eV in CuO and Cu4O3, respectively. This comparison also points towards surface oxidation and reduction effects that can complicate the interpretation of the photoemission spectra.« less

  7. 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.

  8. Temperature- and gaseous phase-mediated reorganization and paramagnetic doping of solid aluminum fluorides: ESR and ab initio quantum chemical studies

    SciTech Connect

    Scholz, G.

    1998-08-01

    Based on cw-X-band ESR spectroscopic measurements of Mn{sup 2+} doped AlF{sub 3} powder samples and DFT (B3LYP)/6-31+G{sup *} quantum chemical calculations it is shown that structural reorganization of AlF{sub 3} (AlF{sub 3} (amorphous) {yields} AlF{sub 3} (crystalline)) are necessarily assisted by chemical reactions with the precipitation of water. It could be unambiguously demonstrated that Mn{sup 2+} ions are suitable spin probes for reorganization processes from amorphous to local crystalline regions in fluoride matrices. The resolution of the {sup 55}Mn-{sup 19}F- superhyperfine structure (both the formation of regular MnF{sub 6}{sup 4{minus}}-species as well as the reduction of strain effects by transformation of the amorphous parts) is a sensitive indicator of the formation of local crystalline regions. DFT(B3LYP)/6-31+G{sup *} calculations of (AlF{sub 3}){sub n}(H{sub 2}O){sub m} complexes (n: 1,2; m: 1--3) resulted in first and acceptable ideas of structures, energetical stabilities, and vibrational frequencies of hydrated AlF{sub 3}. The calculated strength of the Al-O bond, resulting in the stable {l_brace}AlF{sub 3}-OH{sub 2}{r_brace} subunit, and the favored splitting of Al-F-Al bonds by H{sub 2}O molecules, are the main reasons for the immediate and spontaneous hydration of freshly prepared amorphous AlF{sub 3}. Independent of the size of the model complexes, stable substructures like {l_brace}AlF{sub 3}-H{sub 2}O{r_brace} and {l_brace}F{sub 3}AlFAlF{sub 2}-OH{sub 2}{r_brace} can be recognized in all optimized structure models.

  9. 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.

  10. Structural insights on biologically relevant cationic membranes by ESR spectroscopy.

    PubMed

    Rozenfeld, Julio H K; Duarte, Evandro L; Oliveira, Tiago R; Lamy, M Teresa

    2017-08-23

    Cationic bilayers have been used as models to study membrane fusion, templates for polymerization and deposition of materials, carriers of nucleic acids and hydrophobic drugs, microbicidal agents and vaccine adjuvants. The versatility of these membranes depends on their structure. Electron spin resonance (ESR) spectroscopy is a powerful technique that employs hydrophobic spin labels to probe membrane structure and packing. The focus of this review is the extensive structural characterization of cationic membranes prepared with dioctadecyldimethylammonium bromide or diC14-amidine to illustrate how ESR spectroscopy can provide important structural information on bilayer thermotropic behavior, gel and fluid phases, phase coexistence, presence of bilayer interdigitation, membrane fusion and interactions with other biologically relevant molecules.

  11. Light-induced ESR centres in single crystal rutile

    NASA Astrophysics Data System (ADS)

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

    1983-04-01

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

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

    PubMed

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

    2014-06-01

    This paper continues analyses on organic compounds for application in neutron dosimetry performed through electron spin resonance (ESR). Here, the authors present the results obtained by ESR measurements of a blend of ammonium tartrate dosemeters and gadolinium oxide (5 % by weight). The choice of low amount of Gd is due to the need of improving neutron sensitivity while not significantly influencing tissue equivalence. A study of the effect of gadolinium presence on tissue equivalence was carried out. The experiments show that the neutron sensitivity is enhanced by more than an order of magnitude even with this small additive content. Monte Carlo simulations on the increment of energy release due to gadolinium presence were carried, and the results were in good agreement with the experimental data. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  13. Esr1(+) cells in the ventromedial hypothalamus control female aggression.

    PubMed

    Hashikawa, Koichi; Hashikawa, Yoshiko; Tremblay, Robin; Zhang, Jiaxing; Feng, James E; Sabol, Alexander; Piper, Walter T; Lee, Hyosang; Rudy, Bernardo; Lin, Dayu

    2017-09-18

    As an essential means of resolving conflicts, aggression is expressed by both sexes but often at a higher level in males than in females. Recent studies suggest that cells in the ventrolateral part of the ventromedial hypothalamus (VMHvl) that express estrogen receptor-α (Esr1) and progesterone receptor are essential for male but not female mouse aggression. In contrast, here we show that VMHvl(Esr1+) cells are indispensable for female aggression. This population was active when females attacked naturally. Inactivation of these cells reduced female aggression whereas their activation elicited attack. Additionally, we found that female VMHvl contains two anatomically distinguishable subdivisions that showed differential gene expression, projection and activation patterns after mating and fighting. These results support an essential role of the VMHvl in both male and female aggression and reveal the existence of two previously unappreciated subdivisions in the female VMHvl that are involved in distinct social behaviors.

  14. 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}.

  15. Synthesis, Spectral Characterization, DNA/ Protein Binding, DNA Cleavage, Cytotoxicity, Antioxidative and Molecular Docking Studies of Cu(II)Complexes Containing Schiff Base-bpy/Phen Ligands.

    PubMed

    Anupama, Berelli; Aruna, Airva; Manga, Vijjulatha; Sivan, Sreekanth; Sagar, Madamsetty Vijay; Chandrashekar, Ravula

    2017-05-01

    Ternary Cu(II) complexes [Cu(II)(L)(bpy)Cl] 1, [Cu(II)(L)(Phen)Cl] 2 [L = 2,3-dimethyl-1-phenyl-4(2 hydroxy-5-methyl benzylideneamino)-pyrazol-5-one, bpy = 2,2(') bipyridine, phen =1,10 phenanthroline) were synthesized and characterized by elemental analyses, UV-Visible, FT-IR, ESR, Mass, thermogravimetric and SEM EDAX techniques. The complexes exhibit octahedral geometry. The interaction of the Cu(II) with cailf thymus DNA (CT-DNA) was explored by using absorption and fluorescence spectroscopic methods. The results revealed that the complexes have an affinity constant for DNA in the order of 10(4) M(-1) and mode of interaction is intercalative mode. The DNA cleavage study showed that the complexes cleaved DNA without any external agent. The interaction of Cu(II) complexes with bovine serum albumin (BSA) was also studied using absorption and fluorescence techniques. The cytotoxic activity of the Cu(II) complexes was probed in HeLa (human breast adenocarcinoma cell line), B16F10 (Murine melanoma cell line) and HEPA1-6 celllines, complex 1 has good cytotoxic activity which is comparable with the doxarubicin drug, with IC50 values ranging from 3 to 12.6 μM. A further molecular docking technique was employed to understand the binding of the complexes towards the molecular target DNA. Investigation of the antioxidative properties showed that the metal complexes have significant radical scavenging activity potency against DPPH radical.

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

    PubMed

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

    2016-09-28

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

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

    PubMed Central

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

    2017-01-01

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

  18. 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.

  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. Rapid screening for anthocyanins in cane sugars using ESR spectroscopy.

    PubMed

    Thamaphat, Kheamrutai; Goodman, Bernard A; Limsuwan, Pichet; Smith, Siwaporn Meejoo

    2015-03-15

    Anthocyanin, which is soluble in water and released into sugar steam during extraction, was investigated in this study. The anthocyanin content in refined sugar, plantation white sugar, soft brown sugar and raw sugar was determined using electron spin resonance (ESR) spectroscopy, which was operated at room temperature, and compared with spectra from standard anthocyanin. The ESR spectra of red and violet anthocyanins was predominantly g ≈ 2.0055, which corresponded to an unpaired electron located in the pyrylium ring. Signals for Fe(III) and Mn(II), which naturally occur in plants, were found in raw sugar, soft brown sugar and standard anthocyanin but were absent from refined sugar and plantation white sugar due to the refining process. In addition, the ESR results were correlated with the apparent colour of the sugar, which was determined using the method of the International Commission for Uniform Methods of Sugar Analysis and inductively coupled plasma optical emission spectroscopy. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. 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.

  2. 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.

  3. Assessment of the validity of the 28-joint disease activity score using erythrocyte sedimentation rate (DAS28-ESR) as a disease activity index of rheumatoid arthritis in the efficacy evaluation of 24-week treatment with tocilizumab: subanalysis of the SATORI study.

    PubMed

    Nishimoto, Norihiro; Takagi, Nobuhiro

    2010-12-01

    As tocilizumab (TCZ) greatly inhibits inflammatory markers, methods of evaluating rheumatoid arthritis (RA) disease activity that include inflammatory markers may overestimate the effect of TCZ treatment. We have evaluated the impact of inflammatory markers on the efficacy of TCZ by comparing the efficacy indicated by the 28-joint disease activity score using erythrocyte sedimentation rate (DAS28-ESR) with that indicated by the clinical and simplified disease activity indexes (CDAI and SDAI, respectively) and the American College of Rheumatology (ACR) core set criteria in a double-blind study of TCZ-the SATORI study. The Spearman correlation coefficient between DAS28-ESR and CDAI was comparable between that at week 24 and that at baseline [correlation coefficient at baseline and week 24 was 0.823 (p < 0.0001) and 0.818 (p < 0.0001), respectively]. A large difference between the DAS28 remission rate and CDAI remission rate was observed at week 24. However, these results are comparable to those of a previous study conducted with non-TCZ-treated patients. Moreover, the same results were obtained in the comparison between the DAS28-ESR and SDAI, even though the SDAI includes an inflammatory parameter as a component. These results confirm that the DAS28-ESR has a validity comparable to that of other methods in terms of evaluating the RA treatment efficacy of TCZ, despite its strong inflammatory marker-inhibiting effects.

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

    NASA Astrophysics Data System (ADS)

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

    2006-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

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

  6. 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:…

  7. 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:…

  8. High-field/high-pressure ESR

    NASA Astrophysics Data System (ADS)

    Sakurai, T.; Okubo, S.; Ohta, H.

    2017-07-01

    We present a historical review of high-pressure ESR systems with emphasis on our recent development of a high-pressure, high-field, multi-frequency ESR system. Until 2000, the X-band system was almost established using a resonator filled with dielectric materials or a combination of the anvil cell and dielectric resonators. Recent developments have shifted from that in the low-frequency region, such as X-band, to that in multi-frequency region. High-pressure, high-field, multi-frequency ESR systems are classified into two types. First are the systems that use a vector network analyzer or a quasi-optical bridge, which have high sensitivity but a limited frequency region; the second are like our system, which has a very broad frequency region covering the THz region, but lower sensitivity. We will demonstrate the usefulness of our high-pressure ESR system, in addition to its experimental limitations. We also discuss the recent progress of our system and future plans.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2004-06-01

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

  11. 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

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

    PubMed

    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 PvuII 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 PvuII 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: [ PvuII; 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.

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

    NASA Astrophysics Data System (ADS)

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

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

  14. 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.

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

    PubMed

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

    2013-01-01

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

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  18. Graphene Growth on Cu Surface: A Theoretical Study

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  20. Synthesis, Structural, DNA Binding and Cleavage Studies of Cu(II) Complexes Containing Benzothiazole Cored Schiff Bases.

    PubMed

    Tejaswi, Somapangu; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Shivaraj

    2016-11-01

    Novel benzothiazole Schiff bases L(1) [1-((4,6-difluorobenzo[d]thiazol-2-ylimino)methyl) naphthalen-2-ol], L(2) [3-((4,6-difluorobenzo[d]thiazol-2-ylimino) methyl)benzene-1,2-diol], L(3) [2-((4,6-difluorobenzo[d]thiazol-2-ylimino)methyl)-5-methoxyphenol], L(4) [2-((4,6-difluorobenzo[d]thiazol-2-ylimino)methyl)-4-chlorophenol] and their binary Cu(II) complexes were synthesized. The structures of all the compounds have been discussed on the basis of elemental analysis, FT-IR, NMR, UV-Visible, ESI-Mass, TGA, ESR, SEM, powder XRD and magnetic moments. Based on the analytical and spectral data a square planar geometry has been assigned to all complexes in which the Schiff bases act as monobasic bidentate ligands, coordinating through the azomethine nitrogen and phenolic oxygen atom. DNA binding ability of these complexes was studied on CT-DNA by using UV-Vis absorption, fluorescence and viscometry. DNA cleavage ability of the complexes was examined on pBR322 DNA by using gel electrophoresis method. All the DNA binding studies reveal that they are good intercalators. The bioefficacy of the ligands and their complexes was examined against the growth of bacteria and fungi in vitro to evaluate their antimicrobial potential. The screening data revealed that the complexes showed more antimicrobial activity than the corresponding free ligands.

  1. 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).

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

    PubMed

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

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M=Cu(II), Ni(II), Co(II); L=3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, (1)H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate). Copyright © 2012 Elsevier B.V. All rights reserved.

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

    PubMed Central

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

    2016-01-01

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

  4. 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.

  5. Detection of the reduced forms of radical adducts on the ESR trace using HPLC-electrochemical detector-ultraviolet absorption detector-electron spin resonance-MS.

    PubMed

    Ikeda, Hideyuki; Iwahashi, Hideo

    2010-05-01

    To detect and identify the electron spin resonance (ESR) silent forms of the alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN) radical adducts, an electrochemical detector (ECD) was employed as a reactor in the HPLC-ECD-UV absorption detector-ESR-MS (HPLC-ECD-UV-ESR-MS). The ECD was employed to regenerate the radical forms from the reduced forms. The reduced forms of the 4-POBN/pentyl radical adducts were analyzed using the HPLC-ECD-UV-ESR-MS. On addition of the ECD applied potential of +0.3 V, a peak appeared on the ESR trace of the HPLC-ECD-UV-ESR-MS analyses, indicating that the radical forms are regenerated from the reduced forms. The HPLC-ECD-UV-ESR-MS analyses were also performed for the reaction mixtures of phenylhydrazine with CuCl(2). Two peaks (peaks I and II) were detected on the UV trace (300 nm) of the HPLC-ECD-UV-ESR-MS. The mass spectra showed that the peak I and peak II compounds are radical and reduced forms of the 4-POBN/phenyl radical adducts under the ECD applied potential of 0.0 V. Peak I was only detected on the ESR trace under the ECD applied potential of 0.0 V. In addition to peak I, peak II appeared on the ESR trace under the ECD applied potential of +0.3 V, indicating that the reduced forms are oxidized to the corresponding radical forms.

  6. Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu{sup -}(cytidine) and Cu{sup -}(uridine)

    SciTech Connect

    Li Xiang; Ko, Yeon-Jae; Wang Haopeng; Bowen, Kit H.; Guevara-Garcia, Alfredo; Martinez, Ana

    2011-02-07

    The copper-nucleoside anions, Cu{sup -}(cytidine) and Cu{sup -}(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu{sup -}(cytidine) and Cu{sup -}(uridine), respectively. According to our calculations, Cu{sup -}(cytidine) and Cu{sup -}(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu{sup -}(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

  7. Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu-(cytidine) and Cu-(uridine)

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H.; Guevara-García, Alfredo; Martínez, Ana

    2011-02-01

    The copper-nucleoside anions, Cu-(cytidine) and Cu-(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu-(cytidine) and Cu-(uridine), respectively. According to our calculations, Cu-(cytidine) and Cu-(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu-(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

  8. 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.

  9. ESR dosimetry of irradiated ascorbic acid.

    PubMed

    Basly, J P; Longy, I; Bernard, M

    1997-09-01

    As an alternative to heat and gas exposure sterilization, ionizing radiation is gaining interest as a sterilization process for medicinal products. The aim of this work was to develop equations to describe the ESR curves versus dose and storage time after gamma irradiation of ascorbic acid. Several ESR data sets previously acquired in this laboratory were adopted to check the performance of the models. Limit of detection and limit of discrimination are respectively 0.5 kGy and 2 kGy for ascorbic acid. Linear regression is applicable for doses lower than 25 kGy. Since the radiation dose selected must always be based upon the bioburden of the products and the Degree of Sterility required (ANSI/AAMI/ISO 11137), doses in the range 5-25 kGy could be investigated and linear regression would appear to be the least expensive route to follow and gives good results. Quadratic fit, power function, exponential function and bi-exponential functions are of more general applicability to predict irradiation dose. Decay kinetics for radicals versus storage were considered. Nonhomogeneous kinetics with time-dependent rate (diffusion-controlled second-order reaction) and bi-exponential function appeared valid to reproduce the experimental data. Discrimination between irradiated and unirradiated ascorbic acid is possible after a storage of 800 days. It is worth noting that, at present, ESR is the only technique which proves to be suitable for identification and quantification purposes in irradiated pharmaceuticals. Moreover, other features such as sensitivity, precision, ease and non-destructive readout make ESR superior to other proposed analytical techniques.

  10. Liquidus Temperatures of Commercial ESR Slags,

    DTIC Science & Technology

    1981-05-01

    refining (ESR) process is calcium fluoride . To obtain the desired slag properties for each melting operation one or more compounds such as lime...magnesium oxide, alumina, s ’ilica and rare earth oxides may be added to the fluoride . Information on the physical and chemical properties of an Immense...the highly reactive nature of the fluoride -based slags, many gaps still remain. For example, most effort has concentrated upon the more commonly used

  11. Retracted: Impact of polymorphisms in the oestrogen receptors alpha and beta (ESR1, ESR2) genes on risk of vasculogenic erectile dysfunction.

    PubMed

    2014-01-01

    The above article from Andrology, 'Impact of polymorphisms in the oestrogen receptors alpha and beta (ESR1, ESR2) genes on risk of vasculogenic erectile dysfunction' by M. R. Safarinejad, A. Taghva, N. Shafiei and S. Safarinejad published online on 20 May 2013 in Wiley Online Library has been retracted by agreement between the journal Editors-in-Chief, Douglas Carrell and Ewa Rajpert-De Meyts and John Wiley and Sons Ltd. The retraction has been decided due to failure by the lead author to verify the data contained in the study, and to provide evidence of the role of co-authors and their institutional affiliations.

  12. 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.

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

    PubMed

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

    2013-05-01

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

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

    SciTech Connect

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

    1991-12-31

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

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

    SciTech Connect

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

    1991-01-01

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

  16. 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)

  17. Studies of Fe-Cu microwires with nanogranular structure

    NASA Astrophysics Data System (ADS)

    Zhukov, A.; García, C.; DelVal, J. J.; Gonzalez, J.; Knobel, M.; Serantes, D.; Baldomir, D.; Zhukova, V.

    2009-01-01

    We report on the fabrication, and structural and magnetic characterization of Cu63Fe37 microwires with granular structure produced by rapid quenching, using the Tailor-Ulitovsky method, from the immiscible alloys. X-ray diffraction study demonstrated that the structure consists of small (6-45 nm) crystallites of Cu and body centred cubic α-Fe. Magnetic properties have been measured in the range of 5-300 K using a SQUID (superconducting quantum interference device) magnetometer. The temperature dependences of the magnetization measured in a cooling regime when no external magnetic field is applied (zero-field cooling) and in the presence of the field (field cooling) show considerable difference below 20 K. This difference could be related to the presence of small α-Fe grains embedded in the Cu matrix. Those α-Fe grains appear to be blocked at temperatures below that at which the maximum of the magnetization is observed in the low temperature range. Significant magnetoresistance (about 7%) has been found in the samples studied. The shape of the observed dependences is typical of a giant magnetoresistance effect.

  18. 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.

  19. 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

  20. 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

  1. ESR detection of the regioisomers due to addition of methoxy and methylthio radicals to fullerene C{sub 70}

    SciTech Connect

    Borghi, R.; Guidi, B.; Lunazzi, L.; Placucci, G.

    1996-08-09

    The authors report ESR studies of three regioisomers of the MeS-C{sub 70}{center_dot} adduct formed by photolysis. A 1:3:3:1 splitting pattern was observed for each regioisomer. A methoxy adduct of C{sub 70} was formed by photolysis of di-tert butyl peroxide in the presence of C{sub 70}, but the ESR spectra were too complicated for interpretation. Photolysis of MeOSSOMe generates an MeO{center_dot} radical which adds to C{sub 60} forming MeO-C{sub 60}{center_dot} which was studied by ESR spectrometry. 11 refs., 3 figs., 1 tab.

  2. 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

  3. Magnetic properties of Cu(m)O(n) clusters: a first principles study.

    PubMed

    Yang, Fan; Sun, Qiang; Ma, L L; Jia, Yu; Luo, S J; Liu, J M; Geng, W T; Chen, J Y; Li, Sa; Yu, Ying

    2010-08-19

    Experimental evidence shows that small Cu(2)O nanoparticles exhibit ferromagnetic or paramagnetic properties, allowing for the promising possibility to recycle the catalyst Cu(2)O easily in wastewater treatment. In this paper, theoretical calculation studying the magnetic property of copper/oxide clusters is reported. A series of Cu(m)O(n) ((m, n) = (4, 1); (4, 2); (4, 5); (16, 15); (28, 15); (44, 15); (28, 27)) clusters were investigated using generalized gradient approximation (GGA) and the Hubbard U (GGA+U) method within density functional theory (DFT). It is found that the electronic structures of bulk Cu(2)O calculated by the GGA and GGA+U are similar. The structures of Cu(m)O(n) ((m, n) = (4, 1); (4, 2); (4, 5)) are all planar. For the bulk-product Cu(m)O(n) ((m, n) = (16, 15); (28, 15); (44, 15); (28, 27)), O atoms prefer to be the outermost atoms. We classified two types of clusters on the basis of their O to Cu atomic ratios. One is O-rich clusters, i.e., Cu(4)O(5), Cu(16)O(15), and Cu(28)O(27). The other is O-poor clusters, i.e., Cu(4)O, Cu(4)O(2), Cu(28)O(15), and Cu(44)O(15). The calculation results show that the O-rich clusters have longer average Cu-Cu bonds and larger binding energy than those of the O-poor ones. More interestingly, the former are magnetic and give ferromagnetic ordering while the latter are nonmagnetic. The hydrogenation of O-terminated clusters can improve its stability but suppress its magnetism. The study may be extremely useful for the potential applications of Cu(2)O nanoparticles in the catalysis and semiconductor fields.

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

    DTIC Science & Technology

    1987-04-01

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

  5. Electrical conductivity studies on CuBr containing Al2O3 particles

    NASA Technical Reports Server (NTRS)

    Dubec, P. M.; Wagner, J. B., Jr.

    1984-01-01

    The conductivity of CuBr was studied and the role of a second phase, Al2O3, dispersed in CuBr was tested. CuBr melts at 493 C and exhibits three phases in the solid state. CuBr is a good ionic conductor with a transport number for copper ions of virtually unity with weighed proportions of the appropriate chemicals used. The CuBr materials were heated above melting point of CuBr, and the samples were sandwiched between copper electrodes. The ac conductivity, was determined at 1 kHz between 25 and 440 C depending on the sample. It was shown that at low temperatures, the conductivity for CuBr (Al2O3) increased by as much as 100, whereas in the beta phase the conductivity of CuBr containing Al2O3 decreased. The electrical conductivity studies are in agreement with earlier data.

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

    NASA Astrophysics Data System (ADS)

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

    2004-08-01

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

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

    PubMed

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

    2013-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-06-01

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

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

    PubMed

    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 10T 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. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. New phase diagram of ideally flat CuO2 plane: Cu-NMR study in Five-layered Cuprates

    NASA Astrophysics Data System (ADS)

    Mukuda, Hidekazu; Abe, Machiko; Shimizu, Sunao; Kitaoka, Yoshio; Iyo, Akira; Kito, Hijiri; Tanaka, Yasumoto; Kodama, Yasuharu; Tokiwa, Kazuyasu; Watanabe, Tsuneo

    2007-03-01

    We report a systematic Cu-NMR study on Hg-, Tl-,Cu-based five-layered high-Tc cuprates. In underdoped HgBa2Ca4Cu5Oy (Hg-1245) with a Tc=72 K, the AFM order is detected with 0.1μB even at two outer planes (OP's) that are responsible for the onset of superconductivity (SC). This is the first microscopic evidence for the uniform mixed phase of AF and SC on a single CuO2 [1]. Recently we found AFM insulating state at low temperatures in disordered fivelayered cuprate Cu-1245, whereas the carrier densities are similar to Hg-1245(OPT) where the AFM metallic state are realized in IP's[2]. This finding reinforces the phase diagram in which the AFM metallic phase exists between AFM insulator and SC states for the case of ideally-flat CuO2 plane without disorder. [1] Mukuda et al., Phys. Rev. Lett. 96,087001 (2006) [2] Mukuda et al., J. Phys. Soc. Jpn., 75, No.12 (2006)

  11. 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

  12. 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.

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

    PubMed

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

    2011-09-01

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

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

    PubMed

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

    2015-02-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

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

  16. Dislocation kinematics: a molecular dynamics study in Cu

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  18. 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.

  19. 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.

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

    DTIC Science & Technology

    1980-09-01

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

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

    PubMed

    Abou-Melha, Khlood Saad

    2012-11-01

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

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

    NASA Astrophysics Data System (ADS)

    Abou-Melha, Khlood Saad

    2012-11-01

    A synthesis of new thiouracil derivative was carried out and deliberately investigated. A new series of complexes was prepared using Ni(II), Pd(II), Pt(IV), Cu(II) and UO2+2 ions. IR spectral data proposed the coordination mod of the ligand towards each metal ion and displays the binegative pentadentate mod as the maximum mod of coordination obtained with Ni(II) and Cu(II) complexes. 1HNMR spectrum of UO2+2 complex in comparing with the free ligand spectrum supports the binegative appearance of the coordinated ligand through the ionization of Cdbnd O and Cdbnd S groups. The electronic spectral data as well as the magnetic moment measurements are coincide with each others to propose the square-planar geometry with Ni(II), Pd(II) and Cu(II) complexes and octahedral geometry with the others. ESR spectrum of Cu(II) complex displays axially symmetric g tensor parameters with g11 > g⊥ > 2.0023 indicating that the d orbital as a ground state with the square-planar geometry. The TG analysis for all isolated complexes were carried out to assert about the presence of water molecules physically or chemically attached with the central atom. The biological study was carried out against different microorganisms as gram negative, gram positive and fungi. The comparable data display the relative priority of Ni(II) complex in comparing with others against all organisms but, the other complexes display activity by the same with the free ligand.

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

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

  6. Interstitial copper defect induced reconstruction of a new ;CuO4; quadrilateral in CaCu3Ti4O12: A first-principles study

    NASA Astrophysics Data System (ADS)

    Xiao, Haibo; Xu, Linfang; Wang, Ruilong; Yang, Changping

    2017-09-01

    The geometric structure, electronic structure and formation energy of CaCu3Ti4O12 (CCTO) with interstitial copper atom have been studied using the density-functional method within the GGA approximation. Result of structural optimization shows that the interstitial Cu-atom (Cu7) prefers to occupy a special location which is symmetrical with an intrinsic copper atom (Cu13) deviated from the normal site. The mulliken analysis indicates the loss of electrons from interstitial atom (Cu7) and Cu13 are only half more of the losing in other copper atom, which reveals a characteristics of covalent bonding between Cu7/Cu13 and surrounding oxygen atoms respectively. Meanwhile, it is found from electron density difference (EDD) and orbital analysis that the introduction of interstitial Cu atom causes prominent structural reconstruction of a new ;CuO4; quadrilateral. Moreover, the new ;CuO4; planar leads to a corresponding electronic reconstruction in the hybridization between Cu7/Cu13 3d and O 2p at the vicinity of fermi surface, for which a new conductive filament channel comes into being. Besides, the formation energies of the interstitial defects in various charge states are corrected with the value of 2.18, -4.17 and -9.46 eV for charge of 0, 1+ and 2+, respectively.

  7. Study of OSL in NaF: Ca,Cu

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

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

    SciTech Connect

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

    1983-01-01

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

  9. Studies on interface between In2O3 and CuInTe2 thin films

    NASA Astrophysics Data System (ADS)

    Ananthan, M. R.; Malar, P.; Osipowicz, Thomas; Kasiviswanathan, S.

    2017-10-01

    Interface between dc sputtered In2O3 and stepwise flash evaporated CuInTe2 films were studied by probing Si/In2O3/CuInTe2 and Si/CuInTe2/In2O3 structures with the help of glancing angle X-ray diffraction, Rutherford backscattering spectrometry and micro-Raman spectroscopy. The results showed that in Si/In2O3/CuInTe2 structure, a ∼20 nm thick interface consisting of In, Cu and O had formed between In2O3 and CuInTe2 and was attributed to the diffusion of Cu from CuInTe2 into In2O3 film. On the other hand, in Si/CuInTe2/In2O3 structure, homogeneity of the underlying CuInTe2 film was found lost completely. An estimate of the masses of the constituent elements showed that the damage was caused by loss of Te from CuInTe2 film during the growth of In2O3 film on Si/CuInTe2.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  11. 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.

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

    DTIC Science & Technology

    1982-09-01

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

  13. Simulation of the ESR injection system

    NASA Astrophysics Data System (ADS)

    Schillinger, Brigitte; Weiland, Thomas; Langenbeck, Bernhard

    1999-05-01

    In order to improve the acceptance of the ESR beam injection system the influence of the fringe field of the main dipole magnet on the ion optics has to be analysed. Therefore, we perform a 3D MAFIA simulation of the dipole magnet and calculate the injection line which enters the radial fringe field in a tangential way. Starting from the given ESR beta function we trace the beam ellipse backwards in order to obtain the phase space requirements near the exit plane of the inflector magnet. Simulated phase space "monitors" defined at the start and the end of the curved reference trajectory give insight in the change of the beam emittance ellipse and indicate if aperture limitations may lead to beam losses. We obtain the second-order mapping of the phase space ellipse by calculating the first- and second-order field coefficients along the curved reference trajectory and solving the differential equations corresponding to each matrix element numerically. After an introduction into the field calculation method and the principles used to get the field index and second-order field coefficients, we will discuss our results and compare them with calculations based on measured field data (Spiller et al., GSI Scientific Report, 1996, p. 165).

  14. Pilot Study of 64Cu(I) for PET Imaging of Melanoma

    DOE PAGES

    Jiang, Lei; Tu, Yingfeng; Hu, Xiang; ...

    2017-05-31

    Currently, 64Cu(II) labeled tracers including 64CuCl2 have been widely applied in the research of molecular imaging and therapy. Human copper transporter 1 (hCTR1) is the major high affinity copper influx transporter in mammalian cells, and specially responsible for the transportation of Cu(I) not Cu(II). Thus, we investigated the feasible application of 64Cu(I) for PET imaging. 64Cu(II) was reduced to 64Cu(I) with the existence of sodium L-ascorbate, DL-Dithiothreitol or cysteine. Cell uptake and efflux assay was investigated using B16F10 and A375 cell lines, respectively. Small animal PET and biodistribution studies were performed in both B16F10 and A375 tumor-bearing mice. Compared withmore » 64Cu(II), 64Cu(I) exhibited higher cellular uptake by melanoma, which testified CTR1 specially influx of Cu(I). But, due to oxidation reaction in vivo, no significant difference between 64Cu(I) and 64Cu(II) was observed through PET images and biodistribution. In addition, radiation absorbed doses for major tissues of human were calculated based on the mouse biodistribution. Radiodosimetry calculations for 64/67Cu(I) and 64/67Cu(II) were similar, which suggested that although melanoma were with high radiation absorbed doses, high radioactivity accumulation by liver and kidney should be noticed for the further application. Thus, 64Cu(I) should be further studied to evaluate it as a PET imaging radiotracer.« less

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

    NASA Astrophysics Data System (ADS)

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

    1995-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

  18. Investigation of a Cu(II)-poly(gamma-glutamic acid) complex in aqueous solution and its insulin-mimetic activity.

    PubMed

    Karmaker, Subarna; Saha, Tapan K; Sakurai, Hiromu

    2007-04-10

    The complexation between cupric ions (Cu(II)) and poly(gamma-glutamic acid) (gamma-PGA) in aqueous solutions (pH 3-11) has been studied by UV-visible absorption and electron spin resonance (ESR) techniques. Formation of the Cu(II)-gamma-PGA complex is confirmed by the observation of the blue shift of the absorption band in the visible region, anisotropic line shapes in the ESR spectrum at room temperature, and a computer simulation of the visible absorption spectrum of the complex. The structure of the Cu(II)-gamma-PGA complex, depending on the pH, has been determined. The in vitro insulin-mimetic activity of the Cu(II)-gamma-PGA complex is examined by determining both inhibition of free fatty acid release and glucose uptake in isolated rat adipocytes treated with epinephrine, in which the concentration of the Cu(II)-gamma-PGA complex for 50% inhibition of free fatty acid release is very similar to that of CuSO4. However, it is significantly lower than that of a previously reported insulin-mimetic bis(3-hydroxypicolinato)copper(II), [Cu(3hpic)2], complex.

  19. 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.

  20. ESR dating of teeth, bones and eggshells excavated at a Paleolithic site of Douara Cave, Syria

    NASA Astrophysics Data System (ADS)

    Kai, A.; Miki, T.; Ikeya, M.

    Teeth, bones and eggshells excavated at a Paleolithic site, Douara Cave in Syria were measured with electron spin resonance (ESR) in their natural state without destructive sample pre-treatment. The total dose of natural radiation (TD) was estimated using the ESR signals of CO 33- radicals ( g⊥ = 2.0024, g∥ = 1.9977) for teeth and bones and those of radicals ( g∥ = 2.0016, g⊥ = 1.9981) for eggshells. Microwave saturation behaviour and thermal annealing of eggshells are studied in detail.

  1. Anisotropy-governed competition of magnetic phases in the honeycomb quantum magnet Na3Ni2SbO6 studied by dilatometry and high-frequency ESR

    NASA Astrophysics Data System (ADS)

    Werner, J.; Hergett, W.; Gertig, M.; Park, J.; Koo, C.; Klingeler, R.

    2017-06-01

    Thermodynamic properties and low-energy magnon excitations of S =1 honeycomb-layered Na3Ni2SbO6 have been investigated by high-resolution dilatometry, static magnetization, and high-frequency electron spin resonance studies in magnetic fields up to 16 T. At TN = 16.5 K, there is a tricritical point separating two distinct antiferromagnetic phases, AF1 and AF2, from the paramagnetic regime. In addition, our data imply short-range antiferromagnetic correlations at least up to ˜5 TN . Well below TN, the magnetic field BC1≈9.5 T is needed to stabilize AF2 against AF1. The thermal expansion and magnetostriction anomalies at TN and BC 1 imply significant magnetoelastic coupling, both of which are associated with a sign change of ∂ L /∂ B . The transition at BC 1 is associated with softening of the antiferromagnetic resonance modes observed in the electron-spin-resonance spectra. The anisotropy gap Δ =360 GHz implies considerable uniaxial anisotropy. We deduce the crucial role of axial anisotropy favoring the AF1 spin structure over the AF2 one. While the magnetostriction data disprove a simple spin-flop scenario at BC 1, the nature of a second transition at BC 2 ≈ 13 T remains unclear. Both the sign of the magnetostriction and Grüneisen analysis suggest that the short-range correlations at high temperatures are of AF2 type.

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

    PubMed

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

    2013-09-01

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

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

    SciTech Connect

    Madden, K.P.; Taniguchi, Hitoshi

    1996-05-02

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

  4. 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).

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

    PubMed

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

    2008-06-25

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

  6. Electronic interactions within composites of polyanilines formed under acidic and alkaline conditions. Conductivity, ESR, Raman, UV-vis and fluorescence studies.

    PubMed

    Dennany, L; Innis, P C; McGovern, S T; Wallace, G G; Forster, Robert J

    2011-02-28

    The properties of two forms of polyaniline (PAni) synthesised under acidic and basic conditions have been investigated both individually and as combined complexes. The PAni polymerised within alkaline media was redox inactive and non-conducting while the PAni emeraldine salt (ES) was electroactive and conducting. Raman, electron spin resonance, UV-Vis and fluorescence spectroscopies were used to monitor the changes in electronic properties of these conducting polymer composites. Solution cast films of alkaline synthesised (A-PAni) with the PAni ES resulted in an increase in the high spin polaron population suggesting that it acts as a pseudodopant. The ability of the A-PAni to increase and maintain the population of the polaron charge carrier was confirmed by UV-vis and Raman spectroscopy. Significantly, the presence of the A-PAni in PAni ES helped to sustain higher electrical conductivities at loading levels that were well below the percolation threshold of an insulating polystyrene sulfonate polymeric oligomer model. Fluorescence studies indicated that the A-PAni was fluorescent. However, mixtures of A-PAni with the PAni ES resulted in quenching of the A-PAni emission. The quenching process was observed to involve both static and dynamic processes, with the static quenching being dominant. These results suggest that the two polymers are strongly associated with each other when in the solid state. In stark contrast, the alkaline synthesized PAni did not influence the electrochemical properties of the emeraldine salt. These results deviate significantly from the expected outcome of the addition of an insulating A-PAni additive and highlight the unusual interactions occurring between PAni and its alkaline analogue.

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

    PubMed

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

    2015-07-22

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

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

    PubMed

    Avaji, Prakash Gouda; Patil, Sangamesh Amarappa

    2009-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

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

    PubMed

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

    2005-05-01

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

  11. Prognostic significance of ESR1 amplification and ESR1 PvuII, CYP2C19*2, UGT2B15*2 polymorphisms in breast cancer patients.

    PubMed

    Markiewicz, Aleksandra; Wełnicka-Jaśkiewicz, Marzena; Skokowski, Jarosław; Jaśkiewicz, Janusz; Szade, Jolanta; Jassem, Jacek; Zaczek, Anna J

    2013-01-01

    Amplification of the ESR1 gene, coding for estrogen receptor alpha, was shown to predict responsiveness to tamoxifen, however its prognostic impact in breast cancer patients has not been thoroughly investigated. Other factors that could contribute to responsiveness to tamoxifen treatment are polymorphisms in ESR1 gene and genes involved in tamoxifen metabolism. The aim of this study was to assess the prognostic role of ESR1 gene dosage in a consecutive group of breast cancer patients and to correlate this feature with clinico-pathological factors. Additionally, ESR1 PvuII, CYP2C19*2 and UGT2B15*2 polymorphisms were analyzed in the tamoxifen-treated subgroup of patients. Primary tumor samples from 281 stage I-III consecutive breast cancer patients were analyzed for ESR1 gene dosage using real-time PCR with locked nucleic acids hydrolysis probes. In the tamoxifen-treated subgroup of patients, ESR1 PvuII, CYP2C19*2 and UGT2B15*2 polymorphism in leukocytes genomic DNA were analyzed. Results were correlated with clinico-pathological factors and with disease-free survival (DFS) and overall survival (OS). ESR1 amplification (with a cut-off level of 2.0) was found in 12% of the entire group of breast cancer patients, and in 18% of the ER-negative subgroup. This feature was associated with decreased DFS both in the entire group (P=0.007) and in the ER-negative subgroup (P=0.03), but not in the tamoxifen-treated patients. Patients with ESR1 PvuII wt/wt genotype and at least one UGT2B15 wt allele had a worse DFS (P=0.03) and showed a trend towards decreased Os (P=0.08) in comparison to patients with ESR1 PvuII wt/vt or vt/vt genotype and UGT2B15 *2/*2 genotype. ESR1 amplification can occur in ER-negative tumors and may carry poor prognosis. In the tamoxifen-treated subgroup, poor prognosis was related to the combined presence of ESR1 PvuII wt/wt and UGT2B15wt/wt or wt/*2 genotype.

  12. 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.

  13. Investigation on association and expression of ESR2 as a candidate gene for boar sperm quality and fertility.

    PubMed

    Gunawan, A; Cinar, M U; Uddin, M J; Kaewmala, K; Tesfaye, D; Phatsara, C; Tholen, E; Looft, C; Schellander, K

    2012-10-01

    ESR2 is involved in oestrogen-related apoptosis in cell cycle spermatogenesis but their effects have not yet confirmed in pig. Therefore, this study was aimed to investigate the association of ESR2 polymorphism with sperm quality and boar fertility traits and to analyse the ESR2 mRNA and protein expressions in boar reproductive tissues. DNA samples from 203 Pietrain (PI) and 100 Pietrain × Hampshire (PIHA) pigs with records of sperm quality [sperm concentration (SCON), motility (MOT), semen volume (VOL), plasma droplet rate (PDR) and abnormal spermatozoa rate (ASR)] and fertility [non-return rate (NRR) and number of piglet born alive (NBA)] traits were available. A SNP in coding region of ESR2 g.35547A>G in exon 5 was associated with MOT and PDR in the PI and with SCON, VOL, MOT and PDR in PIHA population. For mRNA and protein expression study, a total of six boars were divided into two groups with group I (G-I) and group II (G-II) where G-I characterized for relatively a better sperm quality according to the mean of two groups. mRNA expression was higher in brain and testis than that in all parts of epididymis. Both qRT-PCR and western blot analysis revealed that the ESR2 gene expression and protein expression were significantly higher in testis collected from G-II compared with that of G-I boars. Moreover, ESR2 protein localization in germ cell, Leydig and Sertoli cells, epithelial cells and spermatozoa was remarkable, which indicated the important role of ESR2 in spermatogenesis process. These results might shed new light on the roles of ESR2 in spermatogenesis as candidate for boar fertility, but still the lack of association across populations should be considered. © 2011 Blackwell Verlag GmbH.

  14. Low-Temperature Studies of CuFe2S3 and CuFeS2 by ^{63,65}Cu NMR in the Internal Magnetic Field

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    The resonance ^{63,65}Cu NMR spectra in the internal magnetic field in cubanite CuFe2S3 and chalcopyrite CuFeS2 were studied experimentally at 77 K. Using a cluster approach, ab initio evaluation of the electric field gradient (EFG) at the nuclei of copper in both compounds was performed. The calculations were carried out by the self-consistent restricted method of Hartree-Fock with open shells (SCF-LCAO-ROHF). The largest clusters for which calculations were made had a formula of Cu7Fe_{14}S_{29}^n for cubanite and Cu9Fe_{10}S_{28}^n for chalcopyrite, where n is the cluster charge. The best-fit values of the quadrupole parameters (quadrupole frequency ν _Q and the asymmetry parameter of the EFG tensor η )—determined experimentally (ν _Q ≈ 7.30 MHz and η ≈ 0.82) and by calculation (ν _Q ≈ 7.38 MHz and η ≈ 0.87)—were obtained for a cluster Cu7Fe_{14}S_{29}^{10} for cubanite. Similarly, the best-fit values of the quadrupole parameters—determined experimentally (ν _Q ≈ 1.29 MHz and η ≈ 0.34) and by calculation (ν _Q ≈ 1.40 MHz and η ≈ 0.50)—were obtained for a cluster Cu9Fe_{10}S_{28}^{-4} for chalcopyrite. For these clusters, maps of the electron density distribution in the neighborhood of quadrupole nucleus of copper were built. Based on the analysis of the resulting electron density distribution, it is supposed that the bond in these compounds is not quite covalent. Evaluations of the hyperfine interaction constants were made and maps of the spin density distribution in the neighborhood of quadrupole nucleus of copper were built. The energy level diagram calculated in the high-spin ROHF approximation defined chalcopyrite as a compound with a very narrow LUMO-HOMO gap rather well and is consistent with the notion of this compound as a semiconductor.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  16. Gapless superconductivity in overdoped Hg system: Cu-NQR study

    SciTech Connect

    Ohsugi, Shigeki; Tsuchiya, Tetsuo; Koyama, Tadashi; Fueki, Kazuo

    1996-11-01

    The nuclear quadrupole resonance (NQR) investigation of Cu in the overdoped compounds HgBa{sub 2}CuO{sub y} (Hg1201) with Y=4.06 (T{sub c}=92K) and 4.11 (64K) and HgBa{sub 2}CaCu{sub 2}O{sub y} (Hg1212) with y=6.13 (T{sub c}=125K) and 6.21 (117K) was carried out in zero field. From the temperature (T) dependence of the nuclear spin-lattice relaxation time, T{sub 1}, of {sup 63}Cu, the authors discuss a cause of the T{sub c} suppression with decreasing the number of CuO{sub 2} layers.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Becker, James S.; Saxena, Sunil

    2005-10-01

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

  19. 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.

  20. 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

  1. 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.

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

    PubMed

    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 (9.3GHz) electron spin resonance (ESR) technique. The modern red lentil samples were heated in an electrical furnace at increasing temperatures in the range 70-500 degrees 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 degrees C and above 500 degrees C, respectively. Copyright 2009 Elsevier B.V. All rights reserved.

  3. 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.

  4. 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.

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

    SciTech Connect

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

    1991-05-10

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

  6. Phase diagram of high- Tc superconductor: Cu-NMR studies on multi-layered cuprates

    NASA Astrophysics Data System (ADS)

    Mukuda, H.; Abe, M.; Shimizu, S.; Kitaoka, Y.; Iyo, A.; Kodama, Y.; Tanaka, Y.; Tokiwa, K.; Watanabe, T.

    2008-04-01

    A new phase diagram is presented for an ideally flat CuO2 plane through the Cu-NMR studies on five-layered cuprates MBa2Ca4Cu5Oy(M-1245) (M=Hg,Tl,Cu), which includes an antiferromagnetic (AFM) metal phase and a uniform mixing phase of AFM metal and high- Tc superconductivity (HTSC) in an under-doped region. It has been found that a disorder causes a quantum-phase transition from an AFM metal to an insulating state in an under-doped regime in the Cu-1245 where a disorder is introduced via an oxygen-reduced process. This finding reinforces that an AFM metallic phase exists between the AFM insulating phase and the SC phase for the ideally flat CuO2 plane provided that a disorder is absent.

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

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

    SciTech Connect

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

    1991-06-14

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

  9. 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.

  10. 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

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  13. 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.

  14. Synthesis of 15N omega-hydroxy-L-arginine and ESR and 15N-NMR studies for the elucidation of the molecular mechanism of enzymic nitric oxide formation from L-arginine.

    PubMed

    Clement, B; Schnörwangen, E; Kämpchen, T; Mordvintcev, P; Mülsch, A

    1994-12-01

    N omega-Hydroxy-L-arginine (2) was prepared by a multi-stage synthesis; the key step was the addition of hydroxylamine to the protected cyanamide 8. The presence of N-hydroxyguanidines was confirmed, above all, by 15N-NMR investigations. 15N omega-Hydroxy-L-arginine (2) was converted quantitatively to 15NO by NO synthases from macrophages. 15NO was identified by ESR-spectroscopy. These experiments confirm that 15N omega-hydroxy-L-arginine (2) is an intermediate in the biosynthesis of NO from arginine (1) and that the N-hydroxylated N-atom is present in the NO formed.

  15. 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.

  16. Microstructural study on Kirkendall void formation in Sn-containing/Cu solder joints during solid-state aging.

    PubMed

    Liu, Zhi-Quan; Shang, Pan-Ju; Tan, Feifei; Li, Douxing

    2013-08-01

    Kirkendall void formation at the solder/metallization interface is an important reliability concern for Cu conductors and under-bump metallization in microelectronic packaging industry, whose mechanism is still hard to be understood for different individual cases. In the present work, two typical solder/Cu-diffusing couples, eutectic SnIn/Cu and SnBi/Cu, were studied by scanning/transmission electron microscopy to investigate the microstructural evolution and voiding process after soldering and then solid-state aging. It was concluded that Kirkendall voids formed between two sublayers within Cu2(In,Sn) phase in eutectic SnIn/Cu solder joint, whereas they appeared at the Cu3Sn/Cu interface or within Cu3Sn for eutectic SnBi/Cu solder joint. Besides the effect of impurity elements, the morphological difference within one intermetallic compound layer could change the diffusing rates of reactive species, hence resulting in void formation in the reaction zone.

  17. 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

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

    PubMed

    Bagihalli, Gangadhar B; Patil, Sangamesh A

    2010-06-01

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

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

    PubMed

    Oniki, T; Doi, Y

    1983-07-01

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

  20. 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.

  1. 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.

  2. A multireference configuration interaction study of CuB and CuAl molecular constants and photoionization spectra.

    PubMed

    Ferrão, Luiz F A; Spada, Rene F K; Roberto-Neto, Orlando; Machado, Francisco B C

    2013-09-28

    Accurate potential energy curves and molecular constants for the low-lying electronic states of CuX(y) (X = B, Al; y = 0, +1) were investigated using the complete active space self-consistent field/multireference configuration interaction (MRCI) methodology with aug-cc-pV5Z basis set. The photoionization spectra of CuX were computed, showing electron detachment in the region of far ultraviolet. The results complement the previous theoretical characterizations and the few experimental studies. A comparative analysis was carried out concerning the different choices of reference configuration state functions in the MRCI calculations with and without the contribution of scalar relativistic effects. The results obtained with a small reference set adequately constructed are competitive to those using a much larger number of configuration state functions, and also the scalar relativistic effects improve significantly the molecular constants in this kind of system containing a 3d metal atom.

  3. Structural study of Co and Au nanoclusters landed onto Cu

    NASA Astrophysics Data System (ADS)

    Jiménez-Sáez, J. C.; Pérez-Martín, A. M. C.; Jiménez-Rodríguez, J. J.

    2009-05-01

    The process in which nanoclusters of Co and Au at low energy (<1 eV/atom) impinge on a substrate of Cu (0 0 1) has been studied by molecular-dynamics (MD). Particularly our interest is focussed on the crystalline structure of the clusters and on whether the epitaxy is achieved. The atomic interactions are calculated by means of a many-body potential based on the second momentum approximation of tight-binding scheme. The size of the clusters ranges from a few tens to a few hundreds of atoms. Techniques such as the analysis of grains, the calculation of epitaxy factor and the common neighbour analysis (CNA) are methods of analysis, used in this work, capable to determine the crystalline orientation and resemblance of the clusters to the substrate once they have been deposited on it. The number of atoms with fcc structure is explicitly calculated. The high values found, for large clusters, corroborate that part of the original structure of the cluster remains intact. The results obtained can be summarized as follows: whenever epitaxy requires an expansion of the cluster structure to fit the substrate, the process is more effective than the opposite in which a compression is required. The size of the cluster plays an opposite role in the epitaxial process, i.e. the effectiveness to get epitaxy diminishes for large sizes.

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

    PubMed

    Jain, Anuj; Baranwal, Ravi Kant; Bharti, Ajaya; Vakil, Z; Prajapati, C S

    2013-01-01

    Nanostructured zinc-copper mixed ferrite was synthesized using sol-gel method. XRD patterns of different compositions of zinc-copper ferrite, Zn(1-x)Cu(x)Fe2O4 (x = 0.0, 0.25, 0.50, 0.75), revealed single phase inverse spinel ferrite in all the samples synthesized. With increasing copper concentration, the crystallite size was found to be increased from 28 nm to 47 nm. The surface morphology of all the samples studied by the Scanning Electron Microscopy there exhibits porous structure of particles throughout the samples. The pellets of the samples are prepared for LPG sensing characteristics. The sensing is carried out at different operating temperatures (200, 225, and 250°C) with the variation of LPG concentrations (0.2, 0.4, and 0.6 vol%). The maximum sensitivity of 55.33% is observed at 250°C operating for the 0.6 vol% LPG.

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

    NASA Astrophysics Data System (ADS)

    Bioud, Nadhira; Kassali, Kamel; Bouarissa, Nadir

    2017-04-01

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

  6. 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.

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

    SciTech Connect

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

    2014-03-24

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

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

    PubMed

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

    2016-11-09

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

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

    PubMed

    Niemi, L; Minni, E; Ivaska, A

    1986-06-01

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

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

    PubMed

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

    2009-11-21

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

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

    SciTech Connect

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

    2011-12-05

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  14. Electronic structure and magnetism of Mn 2CuAl: A first-principles study

    NASA Astrophysics Data System (ADS)

    Li, S. T.; Ren, Z.; Zhang, X. H.; Cao, C. M.

    2009-07-01

    The electronic structure and magnetism of a new Mn-based Heusler alloys Mn 2CuAl has been studied by first-principles calculations. The calculations suggest that Mn 2CuAl crystallizes in the Hg 2CuTi type of structure, in which the Cu atoms have Al as nearest neighbors. As a consequence, the Mn atoms occupy two nearest neighbor sublattices A and B. Like the well known Heusler alloy Cu 2MnAl, the magnetic moment of Mn 2CuAl also comes from the two Mn atoms in the lattice, while the Cu atom is almost nonmagnetic. At equilibrium lattice constant, Mn 2CuAl is a ferrimagnet with moment of 0.22μ B. The partial spin moments of Mn (A) and Mn (B) are -3.52μ B and 3.74μ B, respectively. The small total moment comes from the antiparallel configurations of the Mn partial moments. With a small contraction of the lattice, the total moment becomes near zero and a half-metallic antiferromagnetic state is observed.

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

    SciTech Connect

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

    2015-04-01

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

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

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

    PubMed Central

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

    2010-01-01

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

  2. Radiation damage in X-irradiated single crystals of Ph 3P +CH 2SCH 3Cl -: An ESR and ENDOR study of the Ph 3P +CHSCH 3 and Ph 3P +CH 2SS radicals

    NASA Astrophysics Data System (ADS)

    Geoffrey, M.; Reddy, M. V. V. S.

    X irradiation, at room temperature, of a single crystal of Ph 3P +CH 2SCH 3Cl - produces two radical species which are identified from an analysis of their ESR and ENDOR spectra. The resulting 31P, 1H(CH) and 1H(CH 3) hyperfine coupling tensors show that one of these radicals is Ph 3P +CHSCH 3. The g tensor and the 1H and 31P coupling tensors obtained for the second radical lead to the identification of Ph 3P +CH 2SS. It is shown that, for this sulfur centered radical, the C—P bond makes an angle of ˜ 127 °C with the sulfur π * orbital containing the unpaired electron.

  3. Junction studies on electrochemically fabricated p-n Cu(2)O homojunction solar cells for efficiency enhancement.

    PubMed

    McShane, Colleen M; Choi, Kyoung-Shin

    2012-05-07

    p-n Cu(2)O homojunction solar cells were electrochemically fabricated by consecutively depositing an n-Cu(2)O layer on a p-Cu(2)O layer. In order to better understand the Fermi levels of the electrochemically grown polycrystalline p- and n-Cu(2)O layers and maximize the overall cell performance, the back and front contacts of the Cu(2)O homojunction cells were systematically changed and the I-V characteristics of the resulting cells were examined. The result shows that the intrinsic doping levels of the electrochemically prepared p-Cu(2)O and n-Cu(2)O layers are very low and they made almost Ohmic junctions with Cu metal with which previously studied p-Cu(2)O layers prepared by thermal oxidation of Cu foils are known to form Schottky junctions. The best cell performance (an η of 1.06%, a V(OC) of 0.621 V, an I(SC) of 4.07 mA cm(-2), and a fill factor (ff) of 42%) was obtained when the p-Cu(2)O layer was deposited on a commercially available ITO substrate as the back contact and a sputter deposited ITO layer was used as the front contact on the n-Cu(2)O layer. The unique features of the p-n Cu(2)O homojunction solar cell are discussed in comparison with other Cu(2)O-based heterojunction solar cells.

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

    PubMed

    Chen, Yeong-Renn; Mason, Ronald P

    2002-07-15

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

  5. An investigation of the dosimetric and kinetic properties of sand using ESR and TL techniques.

    PubMed

    Aydaş, Canan; Aydın, Talat

    2015-07-01

    In this research, the general dosimetric and kinetic properties of sand from a beach in southern Turkey were investigated using electron spin resonance (ESR) and thermoluminescence (TL) techniques. The ESR dose response curve presents linear behaviour in the dose range of 250-1000 Gy followed by sublinear behaviour in the dose range of 2-8 kGy. Kinetic behaviors and activation energy of the free radical were also calculated using the data obtained from annealing studies performed at four different temperatures (220, 240, 260 and 280°C). The activation energy value was calculated as 1.47 eV. The long-term fading of the ESR signal at room temperature turned out to be best described by a second-order kinetic decay function. The presence of measurable ESR signal intensity even after a storage period of 90 days was considered as providing an opportunity in the dose estimation of irradiated sand sample. Although the TL glow curve of the natural (unirradiated) sand sample only has a single broad peak at 317°C, the glow curve of the irradiated sample has four glow peaks located at ~115°C, ~156°C, ~231°C and ~308°C and their intensity tends to be increased with absorbed dose.Tmax-Tstop and glow curve fitting results showed that presence of at least five peaks located at ∼116°C, 149°C, 228°C, 306°C and 360°C. This result suggests that the apparently single glow peak D may consist of two or more overlapping glow peaks. According to the thermal fading of the sand sample at room temperature, the TL signal intensities (23°C and 308°C) were found to be quite large after 30 days of storage this allows a more accurate measurement of the glow peak intensity. The additive dose method, variable heating rate method (VHRM), Tmax-Tstop and glow curve fitting method were used to number of peaks, dosimetric properties and kinetic parameters. This study shows that ESR and TL techniques could be successfully used to investigate the kinetics and dosimetric properties of sand

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  7. Growth and microtopographic study of CuInSe{sub 2} single crystals

    SciTech Connect

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

    2016-05-23

    The CuInSe{sub 2} single crystals were grown by chemical vapour transport (CVT) technique using iodine as transporting agent. The elemental composition of the as-grown CuInSe{sub 2} single crystals was determined by energy dispersive analysis of X-ray (EDAX). The unit cell crystal structure and lattice parameters were determined by X-ray diffraction (XRD) technique. The surface microtopographic study of the as-grown CuInSe{sub 2} single crystals surfaces were done to study the defects, growth mechanism, etc. of the CVT grown crystals.

  8. Growth and microtopographic study of CuInSe2 single crystals

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    PubMed

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

    2013-09-21

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

  11. The problems in ESR dating of tooth enamel of Early Pleistocene and the age of Longgupo hominid, Wushan, China

    NASA Astrophysics Data System (ADS)

    Tiemei, Chen; Qi, Chen; Quan, Yang; Yanqiu, Hu

    2001-12-01

    Quite often ESR dating of tooth enamel provides underestimated ages. The factors, which may account for the age suppression are studied. For dating of the samples of Early Pleistocene, thermal fading of the g=2.0018 signal during the burial time may also lead toage underestimation. Isothermal annealing of the g=2.0018 line was studied in this work and a mixed first- and second-order kinetics was observed. Its implication to the practical dating purpose is discussed. It is suggested that if no uranium leakage is detected, ESR EU ages of Early Pleistocene enamel samples should be considered only as the lower limits of the true ages. Combined ESR and magnetic dating of the Longgupo profile, Wushan, China, assigns the Olduvai subchron to the fossil hominid-bearing layers of 7-8 of this profile.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  13. Spin Labeling ESR Investigation of Covalently Bound Residues in Soil

    NASA Astrophysics Data System (ADS)

    Aleksandrova, Olga; Steinhoff, Heinz-Juergen; Klasmeier, Joerg; Schulz, Marcus; Matthies, Michael

    2013-04-01

    Organic xenobiotic chemicals, such as pesticides, biocides and veterinary pharmaceuticals, interact with soil, which results in the simultaneous formations of metabolites, mineralization products, and bound or non-extractable residues (NER). Substances or metabolites with reactive functional groups, such as aniline or phenol, have a tendency to give a larger proportion of NER. Despite numerous studies on NER, the majority of their chemical structures is still unknown. Reversible sequestration and irreversible formation of NER were also observed for veterinary antibiotic pharmaceuticals, after their application to soil with and without manure. For this purpose, we hypothesized a key role of specific functional groups of soil contaminants, via which contaminants are covalently bound to soil constituents, and advance a method of spin labeling ESR investigation of reaction products using a membrane method. Spin labels (SL) represent chemically stable paramagnetic molecules used as molecular labels and molecular probes for testing the covalent binding, structural properties, and molecular mobility of different physical, chemical, and biological systems. In the case of covalent binding of SL, their ESR spectra become broadened. We used stable nitroxide radicals (NR) as SL. These radicals modeled organic chemical contaminants and differed only in one functional group. The paramagnetic SL 4-Amino Tempo (4-amino-2,2,6,6-tetramethyl-1-piperidinylox) differed from Tempo (2,2,6,6-Tetramethylpiperidinooxy) in a substituent at the para-position of the piperidine ring, whereas Aniline Tempo (1-Piperidinyloxy, 2,2,6,-tetramethyl, 6-Aniline) differed from Tempo in an Aniline substituting one CH3 functional group. Before experimental analysis, we tested temporal changes in the concentration of both NR incubated with soil and found that the life-times of them in soil exceeded 3 days. We contaminated and labeled soil samples with NR, adding to soil the aqueous solution, which already

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

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

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

    PubMed

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

    2005-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  18. Study on multicaloric effect of CuO induced multiferroic

    NASA Astrophysics Data System (ADS)

    Kumar, Amit; Yadav, K. L.

    2014-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1996-11-01

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

  20. CRYRING@ESR: present status and future research

    NASA Astrophysics Data System (ADS)

    Lestinsky, M.; Bräuning-Demian, A.; Danared, H.; Engström, M.; Enders, W.; Fedotova, S.; Franzke, B.; Heinz, A.; Herfurth, F.; Källberg, A.; Kester, O.; Litvinov, Y.; Steck, M.; Reistad, D.; Simonsson, A.; Skeppstedt, Ö.; Stöhlker, T.; Vorobjev, G.; the CRYRING@ESR working Group

    2015-11-01

    The former storage ring CRYRING has been shipped from the Manne Siegbahn Laboratory in Stockholm to Darmstadt as a Swedish in-kind contribution to FAIR. At its new location downstream of ESR all ion species presently accessible in ESR can be transferred to CRYRING, in which ions with rigidities between 1.44 and 0.054 Tm can be stored. The original Swedish layout has been modified by reconfiguring the sequence of straight sections and by slightly increasing the circumference to ESR/2. Ions can be injected from ESR or from an independent 300 keV/u RFQ test injector. The instrumentation of the ring includes an RF drift tube system for acceleration and deceleration (1 T s-1, with a possibility for an upgrade to 7 T s-1), electron cooling, a free experimental section, and both fast and slow extraction of ions. We report on the present progress of this project, give a prospective timeline, and summarize the new research which will be enabled by this project. First beam for commissioning of the storage ring is expected for 2015, final bakeout to restore ultrahigh vacuum conditions in 2016 and ion beams injected through ESR in ˜2017.

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

    PubMed

    van Nes, Solveig; Andersen, Øivind

    2006-12-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  4. ESR spectroscopy of the C60 cation produced by photoinduced electron transfer

    PubMed

    Dunsch; Ziegs; Siedschlag; Mattay

    2000-10-02

    In this study the existence of the C60 cation produced by photochemically induced electron transfer in the presence of different sensitising molecules is proved for the first time by using ESR spectroscopy. It is demonstrated for triphenylpyryliumtetrafluoroborate (TPP) by this spectroscopic method that the electron transfer from C60 to TPP occurs without an application of a cosensitiser. Furthermore it is shown that the addition of alcohols causes a new radical in the system C60/TPP. The stationary concentration of the C60 cation diminishes even in the presence of a cosensitiser to such a low concentration that it is not detectable by ESR spectrosopy. The spectroscopic study of the sensitiser/C60 system is also extended to the reaction products.

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

    SciTech Connect

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

    2014-01-06

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

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-02-01

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

  8. Physical properties of the tetragonal CuMnAs: A first-principles study

    NASA Astrophysics Data System (ADS)

    Máca, F.; Kudrnovský, J.; Drchal, V.; Carva, K.; Baláž, P.; Turek, I.

    2017-09-01

    Electronic, magnetic, and transport properties of the antiferromagnetic (AFM) CuMnAs alloy with tetragonal structure, promising for the AFM spintronics, are studied from first principles using the Vienna ab initio simulation package. We investigate the site occupation of sublattices and the lattice parameters of three competing phases. We analyze the factors that determine which of the three conceivable structures will prevail. We then estimate formation energies of possible defects for the experimentally prepared lattice structure. MnCu and CuMn antisites as well as Mn ↔Cu swaps and vacancies on Mn or Cu sublattices were identified as possible candidates for defects in CuMnAs. We find that the interactions of the growing thin film with the substrate and with vacuum as well as the electron correlations are important for the phase stability while the effect of defects is weak. In the next step, using the tight-binding linear muffin-tin orbital method for the experimental structure, we estimate transport properties for systems containing defects with low formation energies. Finally, we determine the exchange interactions and estimate the Néel temperature of the AFM-CuMnAs alloy using the Monte Carlo approach. A good agreement of the calculated resistivity and Néel temperature with experimental data makes it possible to draw conclusions concerning the competing phases.

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  10. Carbon disulfide (CS2) adsorption and dissociation on the Cu(100) surface: A quantum chemical study

    NASA Astrophysics Data System (ADS)

    Wang, Wenju; Fan, Lili; Wang, Guoping

    2017-08-01

    Density functional theory (DFT) is used to examine the adsorption and dissociation of CS2 on the Cu(100) surface. This study evaluates the adsorption energies and geometries of the species (CS2, CS, C and S) adsorption on the Cu(100) surface, as well as that coadsorption of CS and a S atom, and that coadsorption of C atom and two S atoms. The results indicate that the species (CS2, CS, C and S) are strongly chemadsorbed on the Cu(100) surface through the Csbnd Cu and/or Ssbnd Cu bond with an increased adsorption energy (C/S/S > S/CS > CS2). Two pathways for CS2 dissociation on the Cu(100) surface are constructed, and the energy barrier and reaction energy of each step are calculated. It shows that the dissociated energy barrier of the second Csbnd S bond is 0.25 eV higher than that of the first Csbnd S bond in the pathway 1, but in the pathway 2, the dissociated energy barrier of the second Csbnd S bond is 0.11 eV lower than that of the first Csbnd S bond. Comparing the highest dissociated energy barrier of pathway 1 (0.68 eV) and pathway 2 (0.5 eV), the structure of S/C/S(II) is regarded as a preferable product for the dissociation of CS2 on the Cu(100) surface.

  11. X-ray-absorption studies of YBa2Cu3O7-δ and GdBa2Cu3O7-δ superconductors

    NASA Astrophysics Data System (ADS)

    Boyce, J. B.; Bridges, F.; Claeson, T.; Howland, R. S.; Geballe, T. H.

    1987-10-01

    X-ray-absorption measurements of the high-Tc superconductors YBa2Cu3O7-δ and GdBa2Cu3O7-δ show that their near edge and extended fine structures (EXAFS) are essentially identical over the temperature range of 4.2 to 688 K. The results indicate that not only are YBa2Cu3O7-δ and GdBa2Cu3O7-δ very similar to each other in local bonding and electronic structure, but also remain virtually unchanged, electronically and structurally, over this wide range in temperature, from far below to well above Tc. The positions of the Cu near-edge spectra for these superconductors indicate a Cu valence between that of Cu in CuO, which has a formal valence of II, and that in KCuO2, with a formal valence of III. Our EXAFS structural results agree well with those from neutron diffraction data. Recently proposed alternate structures are shown to be inconsistent with our data. The characteristic vibration frequencies of the near-neighbor atoms show that the two-dimensional Cu-O planes and the one-dimensional Cu-O chains form the most rigid parts of the structure, and these layers are bound more weakly along the c axis via the Ba and Y planes. These oscillator frequencies are identified with specific near-neighbor pairs, and the values are consistent with those for some of the modes seen by inelastic neutron scattering as well as by infrared and Raman spectroscopy. No evidence of phonon softening is apparent in any of the phonon modes studied, providing evidence against a strong electron-phonon coupling mechanism.

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

    DOE PAGES

    Adare, A.

    2015-09-23

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

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

    SciTech Connect

    Adare, A.

    2015-09-23

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

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

    SciTech Connect

    PAL, UDAY B.

    1999-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1987-09-01

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

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

    SciTech Connect

    Scheidenberger, Christoph

    2010-08-12

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

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

    SciTech Connect

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

    1990-08-29

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

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

    SciTech Connect

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

    2012-08-01

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

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

    PubMed

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

    2011-12-01

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

  1. Computer enhancement of ESR spectra of magnetite nanoparticles

    NASA Astrophysics Data System (ADS)

    Dobosz, B.; Krzyminiewski, R.; Koralewski, M.; Hałupka-Bryl, M.

    2016-06-01

    We present ESR measurements of non-interacting magnetic nanoparticle systems. Temperature and orientational dependence of ESR spectra were measured for Fe3O4 nanoparticle coated by dextran or oleic acid, frozen in different magnetic field. Several parameters describing magnetic properties such as g-factor, line width, the anisotropy constant were calculated and discussed. The ESR spectra of investigated nanoparticles were also subjected to Computer Resolution Enhancement Method (CREM). This procedure allows to separate a narrow line on the background of the broad line, which presence in this type of materials was recognized in the recent literature and have been further discussed in the paper. CREM is a valuable tool for monitoring of changes on the surface of magnetic core of nanoparticles.

  2. Local Structure Studies of As-Made Cu2ZnSnS4 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Jewell, Leila; Rocco, Sophia; Bridges, Frank; Carter, Sue A.

    2017-06-01

    Though Cu2ZnSnS4 (CZTS) is a promising material for thin-film solar cells, a significant challenge remains in understanding the structures being formed, particularly in nonstoichiometric materials. We use the extended x-ray absorption fine-structure technique to study the local structure and stoichiometry of as-made, Cu-deficient CZTS nanoparticles and present K -edge data and fits for each of the cations (Cu, Zn, and Sn). The data show that all of the metal-S (M -S ) pairs have the bond lengths of the kesterite structure within 0.02 Å, and the pair distribution function is very narrow (σ ˜0.07 Å ). These results preclude significant fractions of other phases with different M -S bond lengths. The data also reveal some Sn second neighbors around Sn, whereas there are none in the stoichiometric kesterite (or stannite) structure. Consequently, Sn antisite defects must be present on Cu or Zn sites; this is not surprising since there is some excess of Sn. More importantly, the second-neighbor Sn-Sn distance is significantly longer than other M -M distances, and the antisite Sn defects must therefore introduce significant disorder within the Cu and Zn sublattices. The largest distortions are found around Cu and are modeled using a strongly broadened (or split) peak distribution for the Cu -Cu /Zn pairs. We also find that excess Zn does not occupy Cu sites but instead, goes onto Sn sites. The samples are best described as a kesterite structure with significant antisite disorder.

  3. Alanine blends for ESR measurements of thermal neutron fluence in a mixed radiation field.

    PubMed

    Marrale, M; Brai, M; Gennaro, G; Triolo, A; Bartolotta, A; D'Oca, M C; Rosi, G

    2007-01-01

    In this paper, the results of a study on the electron spin resonance (ESR) dosimetry to measure thermal neutron fluence in a mixed radiation field (neutron and photons) are presented. The ESR responses of alanine dosemeters with different additives are compared. In particular, the (10)B-acid boric and the Gd-oxide were chosen to enhance the sensitivity of alanine dosemeters to thermal neutrons. Irradiations were carried out inside the thermal column of the TAPIRO reactor of the ENEA center, Casaccia Rome. The main results are a greater neutron sensitivity and a smaller lowest detectable fluence for the dosemeters with gadolinium than for dosemeters of alanine with (10)B, which is well known to be much more sensitive to thermal neutrons than simple alanine.

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

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

    DOE PAGES

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

    2016-01-25

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

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

    SciTech Connect

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

    2016-01-25

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    PubMed

    Yarbaşi, Zeynep; Karabulut, Bünyamin; Karabulut, Abdulhalik

    2009-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Yarbaşı, Zeynep; Karabulut, Bünyamin; Karabulut, Abdulhalik

    2009-03-01

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

  10. Spin Doublet Point Defects in Graphenes: Predictions for ESR and NMR Spectral Parameters.

    PubMed

    Vähäkangas, Jarkko; Lantto, Perttu; Mareš, Jiří; Vaara, Juha

    2015-08-11

    An adatom on a graphene surface may carry a magnetic moment causing spin-half paramagnetism. This theoretically predicted phenomenon has recently also been experimentally verified. The measurements of defect-induced magnetism are mainly based on magnetometric techniques where artifacts such as environmental magnetic impurities are hard to rule out. Spectroscopic methods such as electron spin resonance (ESR) and paramagnetic nuclear magnetic resonance (pNMR) are conventionally used in the development of magnetic materials, e.g., to study paramagnetic centers. The present density functional theory study demonstrates with calculations of the ESR g-tensor and the hyperfine coupling tensors, as well as the pNMR shielding tensor, that these spectroscopies can be used to identify the paramagnetic centers in graphenes. The studied defects are hydrogen and fluorine adatoms on sp(2)-hybridized graphene, as well as hydrogen and fluorine vacancies in the sp(3)-hybridized graphane and fluorographene, respectively. The directly measurable ESR and pNMR parameters give insight into the electronic and atomic structures of these defects and may contribute to understanding carbon-based magnetism via the characterization of the defect centers. We show that missing hydrogen and fluorine atoms in the functionalized graphane and fluorographene, respectively, constitute sp(2)-defect centers, in which the magnetic resonance parameters are greatly enhanced. Slowly decaying adatom-induced magnetic resonance parameters with the distance from the sp(3)-defect, are found in pure graphene.

  11. The 68mCu/68Cu isotope as a new probe for hyperfine studies: The nuclear moments

    NASA Astrophysics Data System (ADS)

    Fenta, A. S.; Pallada, S.; Correia, J. G.; Stachura, M.; Johnston, K.; Gottberg, A.; Mokhles Gerami, A.; Röder, J.; Grawe, H.; Brown, B. A.; Köster, U.; Mendonça, T. M.; Ramos, J. P.; Marsh, B. A.; Day Goodacre, T.; Amaral, V. S.; Pereira, L. M. C.; Borge, M. J. G.; Haas, H.

    2016-09-01

    Time Differential Perturbed Angular Correlation of γ-rays (TDPAC) experiments were performed for the first time in the decay of 68m Cu (6-, 721 \\text{keV}, 3.75 \\text{min}) produced at the ISOLDE facility at CERN. Due to the short half-life of the source isotope, the measurements were carried out online. The intermediate state (2+, 84.1 \\text{keV}, 7.84 \\text{ns}) offers the unique opportunity to study the electromagnetic fields acting at a copper probe in condensed matter via hyperfine interactions. The present work allowed determination of the nuclear moments for this state. The electric quadrupole moment |Q(2+,84.1 \\text{keV})|=0.110(3) \\text{b} was obtained from an experiment performed in Cu2O and the magnetic dipole moment |μ|=2.857(6) μ_\\text{N} from measurements in cobalt and nickel foils. The results are discussed in the framework of shell model calculations and the additivity rule for nuclear moments with respect to the robustness of the N = 40 sub-shell.

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

    NASA Astrophysics Data System (ADS)

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

    1988-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-04-01

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

  14. NQR-NMR studies of higher alcohol synthesis Cu-Co catalysts

    SciTech Connect

    Not Available

    1992-01-14

    Our studies were essentially concerned with analyzing the magnetic character of the Cu-Co catalysts for Cu/Co ratio ranging from 0.2 to 4 (1,2). The results clearly indicate that; (a) as the copper content increases beyond 50% significant intermetallic interactions occur between copper and cobalt; (b) the magnetic character of the bimetallic clusters formed is sensitively dependant on the method of preparation.

  15. Nitrogen addition using a gas blow in an ESR process

    NASA Astrophysics Data System (ADS)

    Yamamoto, S.; Momoi, Y.; Kajikawa, K.

    2016-07-01

    A new nitrogen method for adding in an ESR process using nitrogen gas blown in through the electrode was investigated. Nitrogen gas blown through a center bore of the electrode enabled contact between the nitrogen gas and the molten steel directly underneath the electrode tip. A ɸ 145mm diameter, laboratory-sized PESR furnace was used for the study on the reaction kinetics. Also, we carried out a water-model experiment in order to check the injection depth of the gas blown in the slag. The water model showed that the gas did not reach the upper surface of the molten metal and flowed on the bottom surface of the electrode only. An EPMA was carried out for a droplet remaining on the tip of the electrode after melting. The molten steel from the tip of the electrode shows that nitrogen gas absorption occurred at the tip of the electrode. The mass transfer coefficient was around 1.0x10-2 cm/sec in the system. This value is almost the same as the coefficient at the molten steel free surface.

  16. ESR Investigations on 13C enriched Sc3@C82

    NASA Astrophysics Data System (ADS)

    Rahmer, J.; Mehring, M.; Dorn, H. C.

    2002-10-01

    13C enrichment of Sc3@C82 for the first time allows the resolution of 13C hyperfine satellite lines in the electron spin resonance (ESR) spectra of this material. A simple model is proposed to simulate the spectra. The ESR data is well reproduced under the assumption that two or three carbon atoms have a significantly stronger hyperfine coupling than all other atoms. Relating this result to the geometry of the C3υ cage leads to the conclusion that the electron density is concentrated on the upper hemisphere of the C82 cage.

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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    In the Y-Ba-Cu-O system, YBa2Cu3O(x) phase is produced by the following peritectic reaction: Y2BaCuO5 + liquid yields 2YBa2Cu3O(x). Through the control of processing conditions and starting compositions, it becomes possible to fabricate large crystals containing fine Y2BaCuO5(211) inclusions. Such crystals exhibit Jc values exceeding 10000 A/sq cm at 77 K and 1T. Recently, researchers developed a novel process which can control the volume fraction of 211 inclusions. Elimination of 211 inclusions is also possible. In this study, researchers prepared YBaCuO crystals with and without 211 inclusions using the novel process, and compared flux pinning, flux creep and critical currents. Magnetic field dependence of Jc for YBaCuO crystals with and with 211 inclusions is shown. It is clear that fine 211 inclusions can contribute to flux pinning. It was also found that flux creep rate could be reduced by increasing flux pinning force. Critical current density estimates based on the conventional flux pinning theory were in good agreement with experimental results.

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    In the Y-Ba-Cu-O system YBa2Cu3Ox phase is produced by the following peritectic reaction: Y2BaCuO5 + liquid yields 2YBa2Cu3Ox. Through the control of processing conditions and starting compositions it becomes possible to fabricate large crystals containing fine Y2BaCuO5(211) inclusions. Such crystals exhibit Jc values exceeding 10000 A/sq cm at 77 K and 1T. Recently, researchers developed a novel process which can control the volume fraction of 211 inclusions. Elimination of 211 inclusions is also possible. In this study, researchers prepared YBaCuO crystals with and without 211 inclusions using the novel process and compared flux pinning, flux creep and critical currents. Magnetic field dependence of Jc for YBaCuO crystals with and without 211 inclusions is shown. It is clear that fine 211 inclusions can contribute to flux pinning. It was also found that flux creep rate could be reduced by increasing flux pinning force. Critical current density estimates based on the conventional flux pinning theory were in good agreement with experimental results.

  20. Texture studies of cold rolled steel, Cu and Ni by neutron diffraction

    NASA Astrophysics Data System (ADS)

    Černík, M.; Neov, D.

    2000-03-01

    The submitted contribution deals with texture investigations of some polycrystalline materials subjected to cold rolling process. Using neutron diffraction the texture of rolled steel, Cu and electrolytic Ni having the cubic BCC or FCC lattices were studied. On the basis of pole figures for Fe(1 1 0), Fe(2 0 0), Fe(1 1 2), Cu(1 1 1), Cu(2 0 0), Cu(2 2 0) and Ni(1 1 1), Ni(2 0 0), Ni(2 20), orientation distribution function (ODF) fully describing the texture of individual samples, could be determined (Wenk and Kocks, Metall. Trans. Al8 (1987) 1083; Kallend et al. Mater. Sci. Eng. A132 (1991)). It has been found that cold rolling significantly changes the texture and a complete anisotropy of the original material. Cold rolling as a specific method of metal forming creates in the rolled material a fibrous structure with α and γ fibres.

  1. Study of thermal stability of Cu{sub 2}Se thermoelectric material

    SciTech Connect

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

    2016-05-23

    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 Cu{sub 2}Se 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 Cu{sub 2}Se phase in bare pellet which transforms to pure α-Cu{sub 2}Se 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-Cu{sub 2}Se phase.

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

    SciTech Connect

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

    2016-01-28

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

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

  4. ESR study of the molecular orientation and dynamics of stable organic radicals included in the 1-D organic nanochannels of 2,4,6-tris-4-(chlorophenoxy)-1,3,5-triazine.

    PubMed

    Kobayashi, Hirokazu; Asaji, Tetsuo; Tani, Atsushi

    2012-03-01

    The molecular orientation and dynamics of the organic stable radicals such as 2,2,6,6-tetramethyl-1-piperidinyl-1-oxyl (TEMPO) or 4-hydroxy-TEMPO (TEMPOL) included in the one-dimensional (1-D) organic nanochannels of 2,4,6-tris-4-(chlorophenoxy)-1,3,5-triazine (CLPOT) were investigated by examining the inclusion compounds (ICs) diluted by the co-inclusion of non-radicals using ESR spectroscopy. Spectral simulation showed that the axial rotation of TEMPO or TEMPOL molecules is excited in the nanochannels with activation energies of 8 and 7 kJ mol(-1) , respectively. The rotation axis was estimated to be tilted towards the principal x direction in the axis system of the g-tensor of the respective radicals. This is quite different from that for similar ICs in the nanochannels of tris(o-phenylenedioxy)cyclotriphosphazene (TPP), in which the radicals are axially rotating around the principal axis y of the g-tensor. The difference is attributed to the larger nanospace of the CLPOT nanochannels. Copyright © 2012 John Wiley & Sons, Ltd.

  5. ESR1 mutations affect anti-proliferative responses to tamoxifen through enhanced cross-talk with IGF signaling.

    PubMed

    Gelsomino, Luca; Gu, Guowei; Rechoum, Yassine; Beyer, Amanda R; Pejerrey, Sasha M; Tsimelzon, Anna; Wang, Tao; Huffman, Kenneth; Ludlow, Andrew; Andò, Sebastiano; Fuqua, Suzanne A W

    2016-06-01

    The purpose of this study was to address the role of ESR1 hormone-binding mutations in breast cancer. Soft agar anchorage-independent growth assay, Western blot, ERE reporter transactivation assay, proximity ligation assay (PLA), coimmunoprecipitation assay, silencing assay, digital droplet PCR (ddPCR), Kaplan-Meier analysis, and statistical analysis. It is now generally accepted that estrogen receptor (ESR1) mutations occur frequently in metastatic breast cancers; however, we do not yet know how to best treat these patients. We have modeled the three most frequent hormone-binding ESR1 (HBD-ESR1) mutations (Y537N, Y537S, and D538G) using stable lentiviral transduction in human breast cancer cell lines. Effects on growth were examined in response to hormonal and targeted agents, and mutation-specific changes were studied using microarray and Western blot analysis. We determined that the HBD-ESR1 mutations alter anti-proliferative effects to tamoxifen (Tam), due to cell-intrinsic changes in activation of the insulin-like growth factor receptor (IGF1R) signaling pathway and levels of PIK3R1/PIK3R3. The selective estrogen receptor degrader, fulvestrant, significantly reduced the anchorage-independent growth of ESR1 mutant-expressing cells, while combination treatments with the mTOR inhibitor everolimus, or an inhibitor blocking IGF1R, and the insulin receptor significantly enhanced anti-proliferative responses. Using digital drop (dd) PCR, we identified mutations at high frequencies ranging from 12 % for Y537N, 5 % for Y537S, and 2 % for D538G in archived primary breast tumors from women treated with adjuvant mono-tamoxifen therapy. The HBD-ESR1 mutations were not associated with recurrence-free or overall survival in response in this patient cohort and suggest that knowledge of other cell-intrinsic factors in combination with ESR1 mutation status will be needed determine anti-proliferative responses to Tam.

  6. Electrogenic steps of light-driven proton transport in ESR, a retinal protein from Exiguobacterium sibiricum.

    PubMed

    Siletsky, Sergey A; Mamedov, Mahir D; Lukashev, Evgeniy P; Balashov, Sergei P; Dolgikh, Dmitriy A; Rubin, Andrei B; Kirpichnikov, Mikhail P; Petrovskaya, Lada E

    2016-11-01

    A retinal protein from Exiguobacterium sibiricum (ESR) functions as a light-driven proton pump. Unlike other proton pumps, it contains Lys96 instead of a usual carboxylic residue in the internal proton donor site. Nevertheless, the reprotonation of the Schiff base occurs fast, indicating that Lys96 facilitates proton transfer from the bulk. In this study we examined kinetics of light-induced transmembrane electrical potential difference, ΔΨ, generated in proteoliposomes reconstituted with ESR. We show that total magnitude of ΔΨ is comparable to that produced by bacteriorhodopsin but its kinetic components and their pH dependence are substantially different. The results are in agreement with the earlier finding that proton uptake precedes reprotonation of the Schiff base in ESR, suggesting that Lys96 is unprotonated in the initial state and gains a proton transiently in the photocycle. The electrogenic phases and the photocycle transitions related to proton transfer from the bulk to the Schiff base are pH dependent. At neutral pH, they occur with τ 0.5ms and 4.5ms. At alkaline pH, the fast component ceases and Schiff base reprotonation slows. At pH8.4, a spectrally silent electrogenic component with τ 0.25ms is detected, which can be attributed to proton transfer from the bulk to Lys96. At pH5.1, the amplitude of ΔΨ decreases 10 fold, reflecting a decreased yield and rate of proton transfer, apparently from protonation of the acceptor (Asp85-His57 pair) in the initial state. The features of the photoelectric potential generation correlate with the ESR structure and proposed mechanism of proton transfer. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  8. ESR spectra and thermal diffusivity of Zn-Al layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Ali Ahmed, Abdullah Ahmed; Abidin Talib, Zainal; Hussein, Mohd Zobir bin

    2012-01-01

    Zn-Al-NO3-LDH was synthesized using the co-precipitation method at pH 7±0.1 and ratio Zn/Al=4. The heat treatment of LDH was studied by X-ray diffraction (XRD) and thermogravimetric analysis (TGA/DTG) to investigate the stability of the LDH structure. The in situ electron spin resonance (ESR) spectra of fresh LDH from room temperature up to 190 °C were obtained, which are due to the presence of nitrate radicals in LDH interlayer. ESR spectra of sintered LDH below 200 °C (ex situ ESR spectra) were investigated, which are also due to the nitrate radicals. However, at 200 °C and above, spectra were due to the oxygen vacancies of ZnO, which was formed during the thermal treatment of LDH. Thermal diffusivity of LDH as a function of in situ temperatures results in a nonlinear relation, which is due to the changing water content of LDH when temperature increases. However, thermal diffusivity of LDH as a function of sintered temperatures showed a linear relation and the slope of these data demonstrated the dependency between thermal diffusivity and water content of LDH below 200 °C. For temperature above 180 °C, the thermal diffusivity behavior was mainly due to the ZnO phase in LDH.

  9. Anisotropic conductivity and charge ordering in (TMTTF)2X salts probed by ESR

    NASA Astrophysics Data System (ADS)

    Coulon, Claude; Lalet, Grégory; Pouget, Jean Paul; Foury-Leylekian, Pascale; Moradpour, Alec; Fabre, Jean Marc

    2007-08-01

    Single crystal ESR data on (TMTTF)2X salts are presented. Taking advantage of the large dimensions of the crystals, skin effect is studied through the asymmetry of the ESR resonance lines. When the microwave magnetic field is perpendicular to the stacking axis, a very rich temperature dependence of this asymmetry is found although the three components of the conductivity tensor often exhibit a semiconducting behavior. In particular, we show that anomalies are present when the TMTTF chains experience a Mott localization or a charge ordering. The whole set of data is discussed theoretically in relation with the anisotropy of the electrical conductivity. We show that the crystal orientation and crystal shape are crucial parameters in explaining the experimental results. More precisely, we found that at the charge ordering transition, the largest conductivity anomaly occurs along the transverse b direction, and we provide evidence, through ESR measurements of the conductivity in this direction, of a charge ordering transition at about 50K in (TMTTF)2Br . With the same method, we also show that irradiation kills the charge ordering transition, while deuteration enhances its critical temperature.

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

    NASA Astrophysics Data System (ADS)

    Aljahdali, M.

    2013-08-01

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

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

    NASA Astrophysics Data System (ADS)

    Manam, J.; Das, S.

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

  12. Contribution of polymorphisms in ESR1, ESR2, FSHR, CYP19A1, SHBG, and NRIP1 genes to migraine susceptibility in Turkish population.

    PubMed

    CoŞkun, Salih; Yůcel, Yavuz; Çim, Abdullah; Cengiz, Beyhan; Oztuzcu, Serdar; Varol, Sefer; Özdemir, Hasan H; Uzar, ErtuĞrul

    2016-03-01

    Migraine, a highly prevalent headache disorder, is regarded as a polygenic multifactorial disease. Single-nucleotide polymorphisms (SNPs) in the genes that involved in sex hormone metabolism may comprise risk for migraine, but the results of previous genetic association studies are conflicting. The aim of this study was to evaluate genetic variants in genes involved in oestrogen receptor and oestrogen hormone metabolism in a Turkish population. A total of 12 SNPs in the ESR1, ESR2, FSHR, CYP19A1, SHBG and NRIP1 genes were genotyped in 142 migraine cases and 141 nonmigraine controls, using a BioMark 96.96 dynamic array system. In addition, gene-gene interactions were analysed using generalized multifactor dimensionality reduction (GMDR) methods. According to GMDR analysis, our results indicated that there was a significant association between migraine and gene-gene interaction among the CYP19A1, FSHR, ESR1 and NRIP1. Single-gene variant analysis showed that a significant association was observed between the TT genotype of rs10046 and migraine susceptibility.When the analysis was performed only in women, the GG genotype of rs2229741 was different between migraineurs and controls.When the female migraine patients were divided into two groups, migraine related to menstruation (MRM) or migraine not related to menstruation (MNRM), GG genotype of rs726281 was significantly associated with MRM. These results suggested that rs10046 could play a potential role in migraine susceptibility in Turkish population. Also, the rare GG genotype of rs726281 appears to influence migraine susceptibility in a recessive manner in MRM subgroup of female patients. In addition, variant GG genotype of rs2229741 may reduce the risk of migraine in Turkish women.

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

    NASA Astrophysics Data System (ADS)

    Kandasamy Arulmozhi, Anant

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

  14. Paracoherence studies in Tl 2CaBa 2Cu 2O 8,CaLaBaCu 3O 7-y and CaSmBaCu 3O 7-y

    NASA Astrophysics Data System (ADS)

    Krishnan, H.; Sankaranarayanan, V.; Srinivasan, R.

    1990-08-01

    In ceramic superconductors, where the intergrain coupling is weak, the phase transition at T co corresponds to the temperature at which phase coherence occurs in all the grains. The region between T m, the mid point of the superconducting transition, and T co, the temperature at which the resistivity goes to zero, is called the paracofioerence region. The resistivity behaviour of single phase Tl 2CaBa 2Cu 2O 8, CaLaBaCu 3O 7-y and CaSmBaCu 3O 7-y has been studied in the above region and the results indicate that the excess conductivity varies as (T - T co) -γ.

  15. ESR dosimetry of fossil enamel: some comments about measurement precision, long-term signal fading and dose-response curve fitting.

    PubMed

    Duval, M; Guilarte Moreno, V; Grün, R

    2013-12-01

    This work deals with the specific studies of three main sources of uncertainty in electron spin resonance (ESR) dosimetry/dating of fossil tooth enamel: (1) the precision of the ESR measurements, (2) the long-term signal fading the selection of the fitting function. They show a different influence on the equivalent dose (D(E)) estimates. Repeated ESR measurements were performed on 17 different samples: results show a mean coefficient of variation of the ESR intensities of 1.20 ± 0.23 %, inducing a mean relative variability of 3.05 ± 2.29 % in the D(E) values. ESR signal fading over 5 y was also observed: its magnitude seems to be quite sample dependant but is nevertheless especially important for the most irradiated aliquots. This fading has an apparent random effect on the D(E) estimates. Finally, the authors provide new insights and recommendations about the fitting of ESR dose-response curves of fossil enamel with a double saturating exponential (DSE) function. The potential of a new variation of the DSE was also explored. Results of this study also show that the choice of the fitting function is of major importance, maybe more than the other sources previously mentioned, in order to get accurate final D(E) values.

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

    PubMed

    Oeschger, Raphael J; Chen, Peter

    2017-01-25

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

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

    PubMed

    Chong Leong, Gan; Uda, Hashim

    2013-01-01

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

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

    PubMed

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

    2010-06-15

    Baker's yeast biomass was pretreated by ethanol and caustic soda, and then the pristine baker's yeast, ethanol pretreated baker's yeast (ethanol-baker's yeast) and caustic soda pretreated baker's yeast (caustic-baker's yeast) were utilized as biosorbents to adsorb Cu(2+) in aqueous solution. The influence of different parameters on Cu(2+) uptake by the three biomasses, such as initial Cu(2+) concentration, initial pH of solution, contact time and temperature, was studied. The mechanism of Cu(2+) binding by biomass was investigated by a number of techniques. Evidence from potentiometric titration revealed that the concentration of carboxyl and amino groups is higher on the caustic and ethanol-baker's yeast compared to the pristine baker's yeast and FTIR spectra confirmed carboxyl, and amino groups on the surface of baker's yeast could be available for characteristic coordination bonding with Cu(2+). In addition, SEM and Zeta potential of the three samples show that caustic and ethanol-pretreatment resulted in the change of baker's yeast surface structure and charge which is relative to adsorption. These results demonstrate that the increase of biosorption capacity for Cu(2+) by ethanol and caustic-baker's yeast was attributed to the increase and exposure of carboxyl and amino groups on the surface of biomass sample. Copyright 2010 Elsevier B.V. All rights reserved.

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

    SciTech Connect

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

    2016-04-09

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

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

    DOE PAGES

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

    2016-04-09

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

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

    SciTech Connect

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

    1999-03-01

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

  2. Cued uncertainty modulates later recognition of emotional pictures: An ERP study.

    PubMed

    Lin, Huiyan; Xiang, Jing; Li, Saili; Liang, Jiafeng; Zhao, Dongmei; Yin, Desheng; Jin, Hua

    2017-06-01

    Previous studies have shown that uncertainty about the emotional content of an upcoming event modulates event-related potentials (ERPs) during the encoding of the event, and this modulation is affected by whether there are cues (i.e., cued uncertainty) or not (i.e., uncued uncertainty) prior to the encoding of the uncertain event. Recently, we showed that uncued uncertainty affected ERPs in later recognition of the emotional event. However, it is as yet unknown how the ERP effects of recognition are modulated by cued uncertainty. To address this issue, participants were asked to view emotional (negative and neutral) pictures that were presented after cues. The cues either indicated the emotional content of the pictures (the certain condition) or not (the cued uncertain condition). Subsequently, participants had to perform an unexpected old/new task in which old and novel pictures were shown without any cues. ERP data in the old/new task showed smaller P2 amplitudes for neutral pictures in the cued uncertain condition compared to the certain condition, but this uncertainty effect was not observed for negative pictures. Additionally, P3 amplitudes were generally enlarged for pictures in the cued uncertain condition. Taken together, the present findings indicate that cued uncertainty alters later recognition of emotional events in relevance to feature processing and attention allocation. Copyright © 2017. Published by Elsevier B.V.

  3. Wetting and spontaneous infiltration: the case study of TaC/(Au, Al and Cu) compared to TiC/Cu

    NASA Astrophysics Data System (ADS)

    Aizenshtein, M.; Froumin, N.; Nafman, O.; Frage, N.

    2016-06-01

    Spontaneous infiltration of molten metals in to ceramic skeletons, in the course MMCs' production, is related to improved wetting of the ceramic by metals. TiC is considered a "metal-like" carbide and is supposed to be wetted well by metals through metallic bonding mechanism. Nevertheless, TiC/Cu exhibit an unusual behavior since spontaneous infiltration of molten Cu takes place, while TiC is partially wetted by Cu (θ=90°).In this work we studied the relation between wetting and spontaneous infiltration in the TaC/Au, Al and Cu systems. TaC is also considered a "metal-like" carbide and indeed no chemical interaction was observed at the interfaces of the studied systems.Sessile drop experiments showed almost perfect wetting in the three system but spontaneous infiltration occurred only in the first two (e.g. TaC/Au or Al). Thermodynamic calculation shows the difference between the systems which also has its' influence on the mechanical properties of the MMCs'. Further calculation clarifies the difference between TaC/Cu and TiC/Cu infiltration behavior, but is unable to explain the wetting results differences.Correlation between wetting and spontaneous infiltration in some cases is not straight forward and more studies and calculations on the atomistic level should be done in order to clarify this matter.

  4. Ion Optical Stray Field Analysis of an ESR Dipole

    NASA Astrophysics Data System (ADS)

    Schillinger, B.; Weiland, T.; Langenbeck, B.

    1997-05-01

    The ion optical characteristics of the injection into the ESR are calculated up to second order. The three dimensional model of an ESR dipole magnet forms the basis of our computations. Special efforts have been spent on an accurate approximation of the lateral stray field over a distance of 2m, in which the ion beam enters the ESR dipole tangentially. The reference trajectory and the first and second order transformation coefficients are calculated solving the corresponding differential equations numerically. For this purpose we have developed a new ion optics section as part of the MAFIA postprocessing module P. The differential equations are set up and solved automatically using the simulated magnetic field distribution. The new implemented section is general and allows the easy calculation of beam trajectories and optical characteristics corresponding to arbitrary numerically calculated magnetic fields. As special feature also phase space monitors along a curved reference trajectory can be defined. We will give a short introduction into the method and discuss the results in case of the ESR injection.

  5. Theory of two-dimensional ESR with nuclear modulation

    NASA Astrophysics Data System (ADS)

    Gamliel, Dan; Freed, Jack H.

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

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

    NASA Astrophysics Data System (ADS)

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

    1998-04-01

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

  7. Hindered magnetic order from mixed dimensionalities in CuP2O6

    NASA Astrophysics Data System (ADS)

    Nath, R.; Ranjith, K. M.; Sichelschmidt, J.; Baenitz, M.; Skourski, Y.; Alet, F.; Rousochatzakis, I.; Tsirlin, A. A.

    2014-01-01

    We present a combined experimental and theoretical study of the spin-1/2 compound CuP2O6 that features a network of two-dimensional (2D) antiferromagnetic (AFM) square planes, interconnected via one-dimensional (1D) AFM spin chains. Magnetic susceptibility, high-field magnetization, and electron spin resonance (ESR) data, as well as microscopic density-functional band-structure calculations and subsequent quantum Monte Carlo simulations, show that the coupling J2D≃40 K in the layers is an order of magnitude larger than J1D≃3 K in the chains. Below TN≃8 K, CuP2O6 develops long-range order, as evidenced by a weak net moment on the 2D planes induced by anisotropic magnetic interactions of Dzyaloshinsky-Moriya type. A striking feature of this 3D ordering transition is that the 1D moments grow significantly slower than the ones on the 2D units, which is evidenced by the persistent paramagnetic ESR signal below TN. Compared to typical quasi-2D magnets, the ordering temperature of CuP2O6 TN/J2D≃0.2 is unusually low, showing that weakly coupled spins sandwiched between 2D magnetic units effectively decouple these units and impede the long-range ordering.

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

    USGS Publications Warehouse

    Evans, H.T.

    1979-01-01

    Additional x-ray structure studies on low chalcocite generally confirm the previously reported structure but show that either disorder is present or the true space group is not P21/c but Pc, four of the 96 copper atoms in the monoclinic unit cell taking on twofold (linear) coordination. The crystal structure of djurleite has been solved in space group P21/n, the monoclinic cell having parameters a = 26.897, b = 15.745, and c = 13.565 angstroms; ?? = 90.13??; and a content of 248 copper and 128 sulfur atoms. Of the 62 different copper atoms in the structure, 52 are in threefold, triangular coordination with sulfur, nine in tetrahedral, and one in linear coordination.

  9. Electronic states and growth modes of Zn atoms deposited on Cu(111) studied by XPS, UPS and DFT

    NASA Astrophysics Data System (ADS)

    Koitaya, Takanori; Shiozawa, Yuichiro; Yoshikura, Yuki; Mukai, Kozo; Yoshimoto, Shinya; Torii, Siro; Muttaqien, Fahdzi; Hamamoto, Yuji; Inagaki, Kouji; Morikawa, Yoshitada; Yoshinobu, Jun

    2017-09-01

    Electronic states and growth modes of the Zn-deposited Cu(111) surface at 300 K were quantitatively studied using core-level and valence photoelectron spectroscopies. Both Cu 2p and Zn 2p core-levels shifted to higher binding energy with increasing the amount of deposited Zn up to multilayer. The origin of the core-level shift of Cu 2p was further investigated by density functional theory calculations; the shift of the Cu 2p peak results from the change in the effective electrostatic potential (initial state effect) caused by the formation of Zn-Cu surface alloy, and the increase of coordination numbers of surface Cu atoms by Zn overlayer. The observed valence photoelectron spectra show the formation of the two atomic-layer Zn-Cu alloy up to the Zn coverage of 1 ML, followed by the formation of three-dimensional Zn islands on the alloyed surface at 300 K.

  10. Synthesis, Characterization, and Cu(2+) Coordination Studies of a 3-Hydroxy-4-pyridinone Aza Scorpiand Derivative.

    PubMed

    López-Martínez, Luis M; Pitarch-Jarque, Javier; Martínez-Camarena, Àlvar; García-España, Enrique; Tejero, Roberto; Santacruz-Ortega, Hisila; Navarro, Rosa-Elena; Sotelo-Mundo, Rogerio R; Leyva-Peralta, Mario Alberto; Doménech-Carbó, Antonio; Verdejo, Begoña

    2016-08-01

    The synthesis, acid-base behavior, and Cu(2+) coordination chemistry of a new ligand (L1) consisting of an azamacrocyclic core appended with a lateral chain containing a 3-hydroxy-2-methyl-4(1H)-pyridinone group have been studied by potentiometry, cyclic voltammetry, and NMR and UV-vis spectroscopy. UV-vis and NMR studies showed that phenolate group was protonated at the highest pH values [log K = 9.72(1)]. Potentiometric studies point out the formation of Cu(2+) complexes of 1:2, 2:2, 4:3, 1:1, and 2:1 Cu(2+)/L1 stoichiometries. UV-vis analysis and electrochemical studies evidence the implication of the pyridinone moieties in the metal coordination of the 1:2 Cu(2+)/L1 complexes. L1 shows a stronger chelating ability than the reference chelating ligand deferiprone. While L1 shows no cytotoxicity in HeLa and ARPE-19 human cell lines (3.1-25.0 μg/mL), it has significant antioxidant activity, as denoted by TEAC assays at physiological pH. The addition of Cu(2+) diminishes the antioxidant activity because of its coordination to the pyridinone moiety phenolic group.

  11. Adsorption studies of Cu(II) on Boston fern ( Nephrolepis exaltata Schott cv. Bostoniensis) leaves

    NASA Astrophysics Data System (ADS)

    Rao, Rifaqat Ali Khan; Khan, Umra

    2017-07-01

    Adsorption studies were done on Boston fern leaves for the effective removal of Cu(II) ions from aqueous solution. It has been tested for the first time for heavy metal adsorption from aqueous solution. This promising material has shown remarkable adsorption capacity towards Cu(II) ions which confirm its novelty, ease of availability, non-toxic nature, cheapness, etc., and give the main innovation to the present study. The adsorbent was analyzed by FT-IR, SEM and EDS. The effect of pH, contact time, initial metal ion concentration and temperature on the adsorption was investigated using batch process to optimize conditions for maximum adsorption. The adsorption of Cu(II) was maximum (96 %) at pH 4. The experimental data were analyzed by Langmuir, Freundlich and Tempkin isotherms. The kinetic studies of Cu(II)were carried out at room temperature (30 °C) in the concentration range 10-100 mg L-1. The data obtained fitted well with the Langmuir isotherm and pseudo-second-order kinetics model. The maximum adsorption capacity ( q m) obtained from Langmuir adsorption isotherm was found to be 27.027 mg g-1 at 30 °C. The process was found to be exothermic and spontaneous in nature. The breakthrough and exhaustive capacities were found to be 12.5 and 37.5 mg g-1, respectively. Desorption studies showed that 93.3 % Cu(II) could be desorbed with 0.1 M HCl by continuous mode.

  12. Adsorption studies of Cu(II) on Boston fern (Nephrolepis exaltata Schott cv. Bostoniensis) leaves

    NASA Astrophysics Data System (ADS)

    Rao, Rifaqat Ali Khan; Khan, Umra

    2016-02-01

    Adsorption studies were done on Boston fern leaves for the effective removal of Cu(II) ions from aqueous solution. It has been tested for the first time for heavy metal adsorption from aqueous solution. This promising material has shown remarkable adsorption capacity towards Cu(II) ions which confirm its novelty, ease of availability, non-toxic nature, cheapness, etc., and give the main innovation to the present study. The adsorbent was analyzed by FT-IR, SEM and EDS. The effect of pH, contact time, initial metal ion concentration and temperature on the adsorption was investigated using batch process to optimize conditions for maximum adsorption. The adsorption of Cu(II) was maximum (96 %) at pH 4. The experimental data were analyzed by Langmuir, Freundlich and Tempkin isotherms. The kinetic studies of Cu(II)were carried out at room temperature (30 °C) in the concentration range 10-100 mg L-1. The data obtained fitted well with the Langmuir isotherm and pseudo-second-order kinetics model. The maximum adsorption capacity (q m) obtained from Langmuir adsorption isotherm was found to be 27.027 mg g-1 at 30 °C. The process was found to be exothermic and spontaneous in nature. The breakthrough and exhaustive capacities were found to be 12.5 and 37.5 mg g-1, respectively. Desorption studies showed that 93.3 % Cu(II) could be desorbed with 0.1 M HCl by continuous mode.

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

    PubMed

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

    2017-03-07

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

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

    PubMed Central

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

    2017-01-01

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

  15. Effect of Cu2+ Activation on Interfacial Water Structure at the Sphalerite Surface as Studied by Molecular Dynamics Simulation

    SciTech Connect

    Jin, Jiaqi; Miller, Jan D.; Dang, Liem X.; Wick, Collin D.

    2015-12-10

    In the first part of this paper, an experimental contact angle study of the fresh and Cu2+ activated sphalerite-ZnS surface as well as the covellite-CuS (001) surface is reported describing the increased hydrophobic character of the surface during Cu2+ activation. In addition to these experimental results, the fresh sphalerite-ZnS (110), copper-zinc sulfide-CuZnS2 (110), villamaninite- CuS2 (100), and covellite-CuS (001) surfaces were examined using Molecular Dynamics Simulation (MDS). Our MDS results on the behavior of interfacial water at the fresh sphalerite-ZnS (110), copper-zinc sulfide-CuZnS2 (110), villamaninite-CuS2 (100), and covellite-CuS (001) surfaces include simulated contact angles, water number density distribution, water dipole orientation, water residence time, and hydrogen-bonding considerations. The copper content at the Cu2+ activated sphalerite surface seems to account for the increased hydrophobicity as revealed by both experimental and MD simulated contact angle measurements. The relatively greater hydrophobic character developed at the Cu2+ activated sphalerite surface and at the copper-zinc sulfide surface has been described by MDS, based on the structure of interfacial water and its dynamic properties. L.X.D. acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  16. ESR dating of barite in sea-floor hydrothermal sulfide deposits at Okinawa Trough

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    The temporal change of submarine hydrothermal activities has been an important issue in the aspect of the evolution of hydrothermal systems which is related with ore formation and biological systems sustained by the chemical species arising from hydrothermal activities (Macdonald et al., 1980). With this aspect, Okumura et al. (2010) made the first practical application of ESR (electron spin resonance) dating technique to a sample of submarine hydrothermal barite to obtain preliminary ages, while Kasuya et al. (1991) first pointed out that barite can be used for ESR dating. ESR is a method to observe radicals having unpaired electrons. As natural radiation creates unpaired electrons in minerals, the age is deduced by dividing the natural radiation dose (obtained from the amount of unpaired electrons) by the dose rate which is estimated by the amount of environmental radioactive elements. The samples were taken by the research cruises, NT12-10 and NT11-20 and NT12-06 operated by JAMSTEC from Hatoma, Yoron, Izena, North Iheya, and Yonaguni IV Knolls of Okinawa Trough. The blocks of sulfide deposits were cut into pieces, and about 2.0g was crushed. The samples were soaked in 12M hydrochloric acid, left for approximately 24 hours. Then, 13M nitric acid was added. Finally, after rinsing in distilled water, the sample was filtered and dried. Impurities were removed by handpicking. A X-ray diffraction study was made to confirm that the grains are pure barite. After γ-ray irradiation at Takasaki Advanced Radiation Research Institute, Japan Atomic Energy Agency, they were measured at room temperature with an ESR spectrometer (JES-PX2300) with a microwave power of 1mW, and the magnetic field modulation amplitude of 0.1mT. The equivalent natural radiation doses were obtained from the increase of ESR signal intensity of SO3- by irradiation. The bulk Ra concentration was measured by the low background pure Ge gamma ray spectrometer. Assuming that Ra is populated only in barite

  17. Radiation-induced amorphization of ordered intermetallic compounds CuTi, CuTi sub 2 , and Cu sub 4 Ti sub 3 : A molecular-dynamics study

    SciTech Connect

    Sabochick, M.J. ); Lam, N.Q. )

    1991-03-01

    Solid-state amorphization resulting from the introduction of chemical disorder and point defects in the ordered intermetallic compounds CuTi, CuTi{sub 2}, and Cu{sub 4}Ti{sub 3} was investigated, with use of the isobaric-isothermal molecular-dynamics method in conjunction with embedded-atom potentials. Antisite defects were produced by randomly exchanging Cu and Ti atoms, and vacancies and interstitials were created by removing atoms at random from their normal sites and inserting atoms at random positions in the lattice, respectively. The potential energy, volume expansion, and pair-correlation function were calculated as functions of the numbers of atom exchanges and point defects. The results indicated that, although both chemical disordering and point-defect introduction increased the system energy and volume, the presence of point defects was essential to trigger the crystalline-to-amorphous transition. By comparing the pair-correlation function calculated after the introduction of point defects with that of the quenched liquid alloy, the critical damage dose (in dpa, displacements per atom) for amorphization was estimated for each compound: {similar to}0.7 dpa for CuTi, {similar to}0.5 dpa for CuTi{sub 2}, and {similar to}0.6 dpa for Cu{sub 4}Ti{sub 3}. At the onset of amorphization, the volume expansions were found to be {similar to}1.9%, {similar to}3.7%, and {similar to}1.7% for these respective compounds. In general, the results obtained in the present work are in good agreement with experimental observations.

  18. Local structure analysis of some Cu(II) theophylline complexes

    NASA Astrophysics Data System (ADS)

    David, L.; Cozar, O.; Forizs, E.; Cr ăciun, C.; Ristoiu, D.; B ălan, C.

    1999-10-01

    The CuT 2L 2·2H 2O complexes [T=Theophylline (1,3-dimethylxanthine); L=NH 3, n-propylamine (npa), 2-aminoethanol (ae)] were prepared and investigated by ESR spectroscopy. Powder ESR spectrum of CuT 2(NH 3) 2·2H 2O is axial ( g||=2.255, g⊥=2.059). ESR spectrum of CuT 2(npa) 2·2H 2O with ( g||=2.299, g⊥=2.081) is a superposition of one axial ( g||=2.299, g⊥=2.073) and one isotropic component ( g0≈2.089), in the same amount. The axial spectra of the former complexes are due to a static Jahn-Teller effect ( EJT≈2880 cm -1). ESR spectrum of CuT 2(ae) 2·2H 2O is orthorhombic ( g1c=2.199, g2c=2.095, g3c=2.037). The local symmetries around the Cu(II) ions remain unchanged by DMF solvating, by adsorbing these solutions on NaY zeolite or by lowering the temperature.

  19. A DFT study of Cu nanoparticles adsorbed on defective graphene

    NASA Astrophysics Data System (ADS)

    García-Rodríguez, D. E.; Mendoza-Huizar, L. H.; Díaz, C.

    2017-08-01

    Metal nanoparticles adsorbed on graphene are systems of interest for processes relative to catalytic reactions and alternative energy production. Graphene decorated with Cu-nanoparticles, in particular, could be a good alternative material for electrodes in direct borohydride fuel cells. However our knowledge of this system is still very limited. Based on density functional theory, we have analyzed the interaction of Cun nanoparticles (n = 4, 5, 6, 7, 13) with pristine and defective-graphene. We have considered two types of defects, a single vacancy (SV), and an extended lineal structural defect (ELSD), formed by heptagon-pentagon pairs. Our analysis has revealed the covalent character of the Cun-graphene interaction for pristine- and ELSD-graphene, and a more ionic-like interaction for SV-graphene. Furthermore, our analysis shows that the interaction between the nanoparticles and the graphene is rather local, i.e., only the nanoparticle atoms close to the contact region are involved in the interaction, being the electronic contact region much higher for defective-graphene than for pristine-graphene. Thus, the higher the particle the lower its average electronic and structural distortion.

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

    PubMed

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

    2002-01-01

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

  1. A computational study of structural and magnetic properties of bi- and trinuclear Cu(II) complexes with extremely long Cu-Cu distances

    NASA Astrophysics Data System (ADS)

    Baryshnikov, Gleb V.; Minaev, Boris F.; Baryshnikova, Alina T.; Ågren, Hans

    2017-07-01

    Three recently synthesized copper(II) complexes with aroylhydrazones of trifluoroacetic and benzenecarboxylic acids (Dalton Trans., 2013, 42, 16878) have been computationally investigated by density functional theory within the broken symmetry approximation accounting for empirical dispersion corrections. A topological analysis of electron density distributions has been carried out using Bader's ;quantum theory of atoms in molecules; formalism. The calculated values of spin-spin exchange for the studied dinuclear complexes indicate a very weak ferromagnetic coupling of the unpaired electrons in good agreement with experimental data. At the same time, the trinuclear copper(II) complex possesses a low-spin doublet ground state with one ferromagnetic and two antiferromagnetic spin projections between the triangular-positioned Cu2+ ions. The estimated values of the coupling constants for the spin-spin exchange in this trinuclear complex are in a good agreement with experimental observations. The calculations support a mechanism of exchange coupling through the aromatic links in these strongly spin-separated systems.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  3. A Theoretical Study of Methanol Synthesis from CO(2) Hydrogenation on Metal-doped Cu(111) Surfaces

    SciTech Connect

    Liu P.; Yang, Y.; White, M.G.

    2012-01-12

    Density functional theory (DFT) calculations and Kinetic Monte Carlo (KMC) simulations were employed to investigate the methanol synthesis reaction from CO{sub 2} hydrogenation (CO{sub 2} + 3H{sub 2} {yields} CH{sub 3}OH + H{sub 2}O) on metal-doped Cu(111) surfaces. Both the formate pathway and the reverse water-gas shift (RWGS) reaction followed by a CO hydrogenation pathway (RWGS + CO-Hydro) were considered in the study. Our calculations showed that the overall methanol yield increased in the sequence: Au/Cu(111) < Cu(111) < Pd/Cu(111) < Rh/Cu(111) < Pt/Cu(111) < Ni/Cu(111). On Au/Cu(111) and Cu(111), the formate pathway dominates the methanol production. Doping Au does not help the methanol synthesis on Cu(111). Pd, Rh, Pt, and Ni are able to promote the methanol production on Cu(111), where the conversion via the RWGS + CO-Hydro pathway is much faster than that via the formate pathway. Further kinetic analysis revealed that the methanol yield on Cu(111) was controlled by three factors: the dioxomethylene hydrogenation barrier, the CO binding energy, and the CO hydrogenation barrier. Accordingly, two possible descriptors are identified which can be used to describe the catalytic activity of Cu-based catalysts toward methanol synthesis. One is the activation barrier of dioxomethylene hydrogenation, and the other is the CO binding energy. An ideal Cu-based catalyst for the methanol synthesis via CO{sub 2} hydrogenation should be able to hydrogenate dioxomethylene easily and bond CO moderately, being strong enough to favor the desired CO hydrogenation rather than CO desorption but weak enough to prevent CO poisoning. In this way, the methanol production via both the formate and the RWGS + CO-Hydro pathways can be facilitated.

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

    NASA Astrophysics Data System (ADS)

    Shirane, G.

    1995-02-01

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

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

    PubMed

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

    2017-02-27

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-06-01

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

  7. NQR-NMR studies of higher alcohol synthesis Cu-Co catalysts

    SciTech Connect

    Not Available

    1991-12-17

    Our previous studies (1,2) on the zerofield NMR spectra of Cu/Co catalysts revealed that the method of preparation sensitively influences the magnetic character of the Catalyst. Catalytic studies of the earlier investigators also (3) show similar influence on the product selectivity and indicate reproducible performance is critically dependent on the control and rigor of the preparation technique. To compliment the NMR results, we have made a thorough investigation of the Hysteresis character of the Cu/Co catalysts with the metal ratio varying from 0.2 to 4.0.

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

    PubMed

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

    2014-07-03

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

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

    SciTech Connect

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

    2015-06-24

    First principle calculations based on DFT have been performed to study the interaction of monoatomically thin Cu wire with silicon nanotube in armchair configuration having chirality (6, 6) both by placing it inside (encapsulation) and outside (functionalisation) the tube. The lowest energy for positioning monoatomically thin Cu wire inside and outside surfaces of SiNT were found to possess cohesive energies of 4.03 eV and 4.02 eV respectively and hence the stability of both SiNTs is found to be almost same. However, From the electronic band structures study, the conductance in case of SiNT for the encapsulated and functionalized positioning of the Cu wire have been found to be 2G{sub 0} and 4G{sub 0} respectively showing enhanced conductance for the functionalized SiNT.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    First principle calculations based on DFT have been performed to study the interaction of monoatomically thin Cu wire with silicon nanotube in armchair configuration having chirality (6, 6) both by placing it inside (encapsulation) and outside (functionalisation) the tube. The lowest energy for positioning monoatomically thin Cu wire inside and outside surfaces of SiNT were found to possess cohesive energies of 4.03 eV and 4.02 eV respectively and hence the stability of both SiNTs is found to be almost same. However, From the electronic band structures study, the conductance in case of SiNT for the encapsulated and functionalized positioning of the Cu wire have been found to be 2G0 and 4G0 respectively showing enhanced conductance for the functionalized SiNT.

  11. Neutron scattering study on CuV 2S 4 and CuTi 2S 4

    NASA Astrophysics Data System (ADS)

    Mücksch, M.; Krimmel, A.; Koza, M. M.; Mutka, H.; Horn, S.

    2006-05-01

    The metallic thiospinel CuV 2S 4 shows an enhanced value of the low-temperature specific heat with γ=C/T≈60 mJ/mol K, suggesting magnetic or electronic correlations. To elucidate the nature of this low-temperature phase with respect to possible magnetic fluctuations, inelastic neutron scattering measurements were performed on polycrystalline CuV 2S 4 and CuTi 2S 4. Both compounds show an inelastic response dominated by phonons. The low-energy phonon response of CuTi 2S 4 is centered around 13 meV and depends only weakly on temperature. The corresponding phonon intensity in the low energy transfer region of CuV 2S 4 is centered at around 6 meV ( T=120 K). The center of gravity of this intensity shifts to about 10 meV ( T=1.8 K) below the structural phase transition at T≈90 K .The significant difference in the low-energy phonon response between both compounds, which display the same lattice symmetry at 120 K, and the strong renormalization of the phonon energies below the structural transition might reflect the influence of strong electron-phonon coupling in CuV 2S 4.

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

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

    PubMed

    Teki, Yoshio; Matsumoto, Takafumi

    2011-04-07

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

  14. BARHL1 Is Downregulated in Alzheimer's Disease and May Regulate Cognitive Functions through ESR1 and Multiple Pathways.

    PubMed

    Barh, Debmalya; García-Solano, María E; Tiwari, Sandeep; Bhattacharya, Antaripa; Jain, Neha; Torres-Moreno, Daniel; Ferri, Belén; Silva, Artur; Azevedo, Vasco; Ghosh, Preetam; Blum, Kenneth; Conesa-Zamora, Pablo; Perry, George

    2017-09-28

    The Transcription factor BarH like homeobox 1 (BARHL1) is overexpressed in medulloblastoma and plays a role in neurogenesis. However, much about the BARHL1 regulatory networks and their functions in neurodegenerative and neoplastic disorders is not yet known. In this study, using a tissue microarray (TMA), we report for the first time that BARHL1 is downregulated in hormone-negative breast cancers and Alzheimer's disease (AD). Furthermore, using an integrative bioinformatics approach and mining knockout mouse data, we show that: (i) BARHL1 and Estrogen Receptor 1 (ESR1) may constitute a network that regulates Neurotrophin 3 (NTF3)- and Brain Derived Neurotrophic Factor (BDNF)-mediated neurogenesis and neural survival; (ii) this is probably linked to AD pathways affecting aberrant post-translational modifications including SUMOylation and ubiquitination; (iii) the BARHL1-ESR1 network possibly regulates β-amyloid metabolism and memory; and (iv) hsa-mir-18a, having common key targets in the BARHL1-ESR1 network and AD pathway, may modulate neuron death, reduce β-amyloid processing and might also be involved in hearing and cognitive decline associated with AD. We have also hypothesized why estrogen replacement therapy improves AD condition. In addition, we have provided a feasible new mechanism to explain the abnormal function of mossy fibers and cerebellar granule cells related to memory and cognitive decline in AD apart from the Tau and amyloid pathogenesis through our BARHL1-ESR1 axis.

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

    PubMed

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

    2002-01-28

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

  16. Muon-spin-relaxation study on the Cu-spin state of Bi2Sr2Ca1- xYx(Cu1- yZny)2O8+δ around the hole concentration of 18 per Cu

    NASA Astrophysics Data System (ADS)

    Watanabe, I.; Akoshima, M.; Koike, Y.; Ohira, S.; Nagamine, K.

    2000-12-01

    Muon-spin-relaxation (μSR) measurements were applied to the partially Zn-substituted Bi-2212 system, Bi2Sr2Ca1-xYx(Cu1- yZny)2O8+δ, to study the Cu-spin state in a wide range of the hole concentration, p. Singularity of the magnetic correlation between Cu spins at p~18 per Cu has been confirmed clearly, proving the existence of the so-called ``18 effect'' in the Bi-2212 system. The muon-spin depolarization rate of the Zn-substituted sample with p~18 per Cu (x=0.3125 and y=0.025) at 0.30 K has been found to exhibit nearly a root-square dependence on the magnetic field applied along the initial muon-spin direction. This field dependence can be explained by assuming that a magnetically excited state of Cu spins moves in a one-dimensional direction producing fluctuating internal fields at the muon sites. The present μSR measurements may support the existence of the stripe correlations of spins and holes in the Bi-2212 system also.

  17. Adsorption of self-assembled monolayer on Cu(111): First-principles study

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Cheng, Jiang-Tao; Ma, Shang-Yi; Wang, Hong-De

    2017-08-01

    The density function theory is used to explore the structures of alkyl-thiolate (RS, R=CH3, CF3) monolayer on the Cu(111) surface. By performing the total energy calculations for RS at three possible adsorption sites (fcc, hcp, bridge) with five different coverages (1/12, 1/9, 1/6, 1/4, 1/3), we obtained the stable adsorption configurations of the Cu-RS system. Especially, the effect of Van der Waals interaction on the adsorption configurations was studied by the DFT-D2 method. The work functions for Cu-RS (R=CH3, CF3) systems were calculated, we find that the CH3S adsorbed on the Cu(111) surface decreases the metal work function remarkably, and the work functions strongly depend on the coverage. In the case of the Cu-CF3S system, the results are just the opposite. Thus, controlling the kind and coverage of the surface adsorbates would be an effective technique to tune the work function of the metal.

  18. Studies on the thermal stability of BiCuSeO

    SciTech Connect

    Barreteau, Celine; Berardan, David Dragoe, Nita

    2015-02-15

    BiCuSeO based materials have been reported as very promising thermoelectric materials, with thermoelectric figure of merit values that make them among the best p-type Pb-free polycrystalline thermoelectric materials, and they could be suitable for applications in thermal to electrical power conversion modules in a 300–650 °C temperature range. In this paper, we report on the phase stability and thermal stability of these materials under inert and oxidizing atmosphere and we discuss their actual potential for wide scale applications. We show that although they are stable in inert atmosphere up to 650 °C, with very slow volatilization rate, it is not the case under oxidizing atmosphere, with a quick oxidation starting at a moderate temperature. - Graphical abstract: BiCuSeO oxidation under air, starting below 300 °C. - Highlights: • Decomposition and oxidation mechanisms of BiCuSeO were studied. • BiCuSeO does not volatilize in inert atmosphere up to 650 °C. • BiCuSeO starts oxidizing for temperatures as low as 200 °C.

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

    NASA Astrophysics Data System (ADS)

    Gupta, Dinesh C.; Ghosh, Sukriti

    2017-04-01

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

  20. Density functional study of CaN mono and bilayer on Cu(001)

    SciTech Connect

    Zahedifar, Maedeh; Hashemifar, S. Javad Akbarzadeh, Hadi

    2014-01-15

    Density functional - pseudopotential calculations are performed to provide first-principles insights into magnetic behaviour of bulk CaN and CaN monolayers on Cu(001) in the rock-salt (RS) and zinc-blende (ZB) structures. Our results indicate that both RS- and ZB-CaN exhibit half-metallic ferromagnetism originated from the incomplete 2p shell of the nitrogen ion. In contrast to the bulk CaN, the CaN monolayers on Cu(001) generally favor ZB structure. We argue that the more stable ZB-CaN thin films on Cu(001) are nonmagnetic, because of strong Cu-N bonding at the interface, while the less stable Ca terminated ZB-CaN thin films exhibit half-metallic ferromagnetism. The transition path between the high energy ferromagnetic and the stable nonmagnetic configurations of the ZB-CaN monolayer on Cu(001) are studied by using the nudged elastic band method. We observe a two stages transition and an activation barrier of about 1.18 eV in the minimum energy path of this transition.